Ultraviolet light absorbers

ABSTRACT

The present invention relates to novel ultraviolet light absorbers of the benzoxazinone, oxanilide, benzylidene malonate, quinazoline and benzotriazole classes. The invention also relates to polymer and photographic compositions stabilized against the deleterious effects of light induced degradation which comprise the novel ultraviolet light absorbers.

This application is a divisional of U.S. application Ser. No.10/486,134, which is a 371 of PCT/EP 02/08709, filed Aug. 5, 2002, whichclaims priority of U.S. provisional app. No. 60/312,011, filed Aug. 13,2001, the contents of which applications are hereby incorporated byreference.

The present invention relates to novel ultraviolet light absorbers ofthe benzoxazinone, oxanilide, benzylidene malonate, quinazoline andbenzotriazole classes. The invention also relates to polymer andphotographic compositions stabilized against the deleterious effects oflight induced degradation, which comprise the novel ultraviolet lightabsorbers.

Benzoxazinones

U.S. Pat. Nos. 5,560,852, 5,783,307, 5,558,912, 5,480,926 and 4,444,262,EP 0 993 965 A2 and JP 00192394 disclose certain benzoxazinoneultraviolet light absorbers (UVA's). Examples of benzoxazinones forother uses can be found as in Fenton et al., J. Med. Chem. 1989, 32,265-272 and WO 00/75139 A2. Most known benzoxazinone compounds aremono-substituted or symmetrically substituted.

The known mono-substituted or symmetrically substituted benzoxazinoneUVA's are often associated with photopermanence, compatibility and/orvolatility problems in polymeric substrates. It has been found thatcertain substituents such as alkyl, aralkyl, e.g. cumyl, andperfluoroalkyl provide these compounds with lower volatility and greatercompatibility in a variety of polymeric systems. Other groups such asalkoxy and alkoxy carbonyl, among others, are also found to be useful.Further, it has been found that the permanence of benzoxazinone UVabsorbers is enhanced or diminished depending on the electronic natureand substitution pattern of the substituents.

It has been found that for benzoxazinone compounds such as

that electron withdrawing groups, such as —CF₃, cyano, carboxy ester,and the like, on the phenyl ring (R substituents) improvephotostability, whereas electron rich substituents such as methoxy inthese positions cause a decrease in photostability. This effect isparticularly pronounced when certain other substituents are present onthe benzo ring (R′ groups), such as moderately electron donating groups.For example, it has been found that when at least one R′ is a cumylgroup (1,1-dimethylbenzyl), compatibility is improved while maintaininggood photopermanence.

The benzoxazinone compounds of the present invention are of formula (Ia)or (Ib)

where in formula (Ia)

each R and R′ is independently hydrogen, halogen, straight or branchedchain alkoxy of 1 to 24 carbon atoms, cycloalkoxy of 5 to 12 carbonatoms, perfluoroalkoxy of 1 to 24 carbon atoms, cyano, perfluoroalkyl of1 to 12 carbon atoms, —CO-G₃, —COOG₃, —CONHG₃, —CON(G₃)₂, E₃S—, E₃SO—,E₃SO₂—, nitro, —N(G₃)₂,

G₃ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight or branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,aryl of 6 to 12 carbon atoms, or said aryl or said phenylalkylsubstituted on the aryl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,

or each R and R′ is independently hydroxy, straight or branched chainalkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7to 15 carbon atoms, aryl of 6 to 12 carbon atoms, or said aryl or saidphenylalkyl substituted on the aryl ring by 1 to 4 alkyl of 1 to 4carbon atoms;

or each R and R′ is independently said alkyl of 1 to 24 carbon atoms orsaid alkoxy of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbonatoms substituted by one or more —OH, —COOG₃, —OCOG₃, —OE₄, —NCO,—NHCOG₃ or —NE₇E₈ groups or mixtures thereof, where E₄ is straight orbranched chain alkyl of 1 to 24 carbon atoms or straight or branchedchain alkenyl of 2 to 18 carbon atoms; or said alkyl or said alkenylinterrupted by one or more —O—, —NH— or —NE₄- groups or mixtures thereofand which can be unsubstituted or substituted by one or more —OH, —NH₂or —COOG₃ or mixtures thereof,

or each R and R′ is independently a group of formula

where

E₂₂, E₂₃, E₂₄, E₂₅ and E₂₆ are independently hydrogen, halogen, straightor branched alkyl of 1 to 18 carbon atoms, alkenyl of 2 to 18 carbonatoms, said alkyl or said alkenyl substituted by one or more halogen,—OCOG₃, —OE₄, —NCO, —NHCOG₃ or —NE₇E₈, or mixtures thereof, where E₄ isstraight or branched chain alkyl of 1 to 24 carbon atoms or straight orbranched chain alkenyl of 2 to 18 carbon atoms; or said alkyl or saidalkenyl interrupted by one or more —O—, —NH— or —NE₄- groups or mixturesthereof and which can be unsubstituted or substituted by one or more—OH, or —NH₂, or mixtures thereof; or

E₂₂, E₂₃, E₂₄, E₂₅ and E₂₆ are independently phenyl, phenylalkyl of 7 to15 carbon atoms, —OH, —OCOG₃, —OE₃, —NCO, —NHCOG₃ or —NE₇E₈, cyano,nitro, perfluoroalkyl of 1 to 12 carbon atoms, —COG₃, —COOG₃, —CON(G₃)₂,—CONHG₃, E₃S—, E₃SO—, E₃SO₂—, —SO₂—X₁-E₃;

X₁ is —O—, —NH— or —NE₄-;

E₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbonatoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbonatoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 12 carbon atomsor said aryl substituted by one or two alkyl of 1 to 4 carbon atoms or1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6to 16 carbon atoms,

E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms,C₆-C₁₄aryl, C₇-C₁₅aralkyl, straight or branched chain alkenyl of 2 to 18carbon atoms, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl, or E₇and E₈ together with the N atom are a pyrrolidine, piperidine,piperazine or morpholine ring,

or two adjacent R or R′ groups together may form a 5 to 7 membered ringwhich may be interrupted by —O—, —NG₃- or —S—, which ring may be furthersubstituted by straight or branched chain alkyl of 1-12 carbon atoms,aryl of 6 to 12 carbon atoms or phenylalkyl of 7 to 15 carbon atoms,

where at least one R is halogen, cyano, perfluoroalkyl of 1 to 12 carbonatoms, —CO—G₃, —COOG₃, —CONHG₃, —CON(G₃)₂, E₃SO—, E₃SO₂—, nitro or agroup

where at least one of E₂₂-E₂₆ is halogen, cyano, perfluoroalkyl of 1 to12 carbon atoms, —CO-G₃, —COOG₃, —CONHG₃, —CON(G₃)₂, E₃SO—, E₃SO₂— ornitro; and

where in formula (Ib)

at least one R is cyano or perfluoroalkyl of 1 to 12 carbon atoms andthe remaining R groups are independently

hydrogen, halogen, straight or branched chain alkoxy of 1 to 24 carbonatoms, cycloalkoxy of 5 to 12 carbon atoms, perfluoroalkoxy of 1 to 24carbon atoms, cyano, perfluoroalkyl of 1 to 12 carbon atoms, —CO-G₃,—COOG₃, —CONHG₃, —CON(G₃)₂, E₃S—, E₃SO—, E₃SO₂—, nitro, —N(G₃)₂,

G₃ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight or branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,aryl of 6 to 12 carbon atoms, or said aryl or said phenylalkylsubstituted on the aryl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,

or each R is independently hydroxy, straight or branched chain alkyl of1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 24carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15carbon atoms, aryl of 6 to 12 carbon atoms, or said aryl or saidphenylalkyl substituted on the aryl ring by 1 to 4 alkyl of 1 to 4carbon atoms;

or each R is independently said alkyl of 1 to 24 carbon atoms or saidalkoxy of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atomssubstituted by one or more —OH, —COOG₃, —OCOG₃, —OE₄, —NCO, —NHCOG₃ or—NE₇E₈ groups or mixtures thereof, where E₄ is straight or branchedchain alkyl of 1 to 24 carbon atoms or straight or branched chainalkenyl of 2 to 18 carbon atoms; or said alkyl or said alkenylinterrupted by one or more —O—, —NH— or —NE₄- groups or mixtures thereofand which can be unsubstituted or substituted by one or more —OH, —NH₂or —COOG₃ or mixtures thereof,

or each R is independently a group of formula

where

E₂₂, E₂₃, E₂₄, E₂₅ and E₂₆ are independently hydrogen, halogen, straightor branched alkyl of 1 to 18 carbon atoms, alkenyl of 2 to 18 carbonatoms, said alkyl or said alkenyl substituted by one or more halogen,—OCOG₃, —OE₄, —NCO, —NHCOG₃ or —NE₇E₈, or mixtures thereof, where E₄ isstraight or branched chain alkyl of 1 to 24 carbon atoms or straight orbranched chain alkenyl of 2 to 18 carbon atoms; or said alkyl or saidalkenyl interrupted by one or more —O—, —NH— or —NE₄- groups or mixturesthereof and which can be unsubstituted or substituted by one or more—OH, or —NH₂, or mixtures thereof; or

E₂₂, E₂₃, E₂₄, E₂₅ and E₂₆ are independently phenyl, phenylalkyl of 7 to15 carbon atoms, —OH, —OCOG₃, —OE₃, —NCO, —NHCOG₃ or —NE₇E₈, cyano,nitro, perfluoroalkyl of 1 to 12 carbon atoms, —COG₃, —COOG₃, —CON(G₃)₂,—CONHG₃, E₃S—, E₃SO—, E₃SO₂—, —SO₂—X₁-E₃;

X₁ is —O—, —NH— or —NE₄-;

E₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbonatoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbonatoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 12 carbon atomsor said aryl substituted by one or two alkyl of 1 to 4 carbon atoms or1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6to 16 carbon atoms,

E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms,C₆-C₁₄aryl, C₇-C₁₅aralkyl, straight or branched chain alkenyl of 2 to 18carbon atoms, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl, or E₇and E₈ together with the N atom are a pyrrolidine, piperidine,piperazine or morpholine ring,

or two adjacent R groups together may form a 5 to 7 membered ring whichmay be interrupted by —O—, —NG₃- or —S—, which ring may be furthersubstituted by straight or branched chain alkyl of 1-12 carbon atoms,aryl of 6 to 12 carbon atoms or phenylalkyl of 7 to 15 carbon atoms.

For instance, in the present benzoxazinone compounds of formula (Ia)above, when one of R is nitro, E₃SO₂—, —CO-G₃, —COOG₃, —CONHG₃,—CON(G₃)₂, at least one of R′ is other than hydrogen. For example atleast one of R′ is cumyl.

For example, in the present benzoxazinone compounds of formula (Ia)above, at least one of R is cyano or perfluoroalkyl of 1 to 12 carbonatoms.

For example, at least one of R is —CF₃.

For example, at least one of R is cyano or perfluoroalkyl of 1 to 12carbon atoms and at least one of R′ is cumyl.

For example, more than one of R is halogen, for example 2, 3, 4 or 5 ofR is halogen.

Present benzoxazinones are for example

where

R₁, R₂, R₃ and R₄ are as defined above, in particular R₁ is cumyl or—OCH₃ and one of R₂, R₃ or R₄ is —CF₃ or —COOG₃, for example where: R₁R₂ R₃ R₄ λmax cumyl H H COOCH₃ 293 nm (ε 12500) cumyl H H CF₃ 333 nm (ε18750) cumyl H COOCH₃ H 305 nm (ε 21200) cumyl H CF₃ H 304 nm (ε 20500)cumyl CF3 H H 287 nm (ε 20200) OCH₃ H CF₃ H 316 nm OCH₃ CF₃ H H 291 nmOCH₃ H H CF₃ 318 nmFurther examples are compounds according to formula (Ib) which are forexample of the formula

where

R is independently cyano, perfluoroalkyl of 1 to 12 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, straight or branched chain alkyl of1 to 24 carbon atoms or straight or branched chain alkoxy of 1 to 24carbon atoms,

The compound according to formula (Ib) may for example be of the formula

where

R is —CF₃ or cumyl.

The benzoxazinone compounds of formula (Ia) and (Ib) are useful UV-lightstabilizers for organic materials. Consequently a further aspect of theinvention is a composition comprising

(a) an organic polymer or recording material subject to the adverseeffects of ultraviolet light, and

(b) at least one benzoxazinone compound of formula (Ia) or (Ib).

Oxanilides

The use and preparation of oxanilides as light stabilizers is well knownand described for example in U.S. Pat. Nos. 3,906,041, 4,412,024,5,045,083, 5,969,014 and 5,338,319. The use of oxanilides as ligands fortransition metals are also known is disclosed in WO 98/40374. The use ofcertain unsymmetrical oxanilides (oxalamides) for improving solubilityof the additive in polymer is taught in British Patent Application1,234,128. The use of trifluoroalkyl substitutents, in particulartrifluoromethyl, on symmetrical oxanilides for chargecontrol agents isdiscribed in JP 09179352. The use of trifluoroalkyl substitutedsymmetrical oxanilides for the stabilization of poly(vinyl chloride) isdisclosed in Plast. Massy 1981 51-53 (in Russian) [Chem. Abstr. 1981 95408186]. The preparation of oxanilides containing trifluoromethylsubstituents is discribed in U.S. Pat. No. 3,906,033, French 1 506 632,and French 1 516 276. The phytotoxicity of oxanilides containingtrifluoromethyl substituents has been reported in Farmaco, Ed. Sci. 196722, 717 (in (Italian) [Chem. Abstr. 1968 68 77924]. The properties ofthe unsymmetrical oxanilides of the instant invention have not beenpreviously anticipated, which includes 1) improved solubility, 2)improved compatibility and 3) in the case of the perfluoroalkyarylcompounds: improved molar absorptivity and spectral coverage.Additionally, a novel process for the preparation of theperfluoroalkyaryl compounds is described.

The present oxanilides are of formula (II)

where R is straight or branched chain alkoxy of 12 to 24 carbon atomsand

R₁₆ and R₁₇ are independently hydrogen, perfluoroalkyl of 1 to 12 carbonatoms, cyano, nitro, —CO-G₃, —COOG₃, —CONHG₃, —CON(G₃)₂, E₃S—, E₃SO—,E₃SO₂—,

where both R₁₆ and R₁₇ are not hydrogen,

G₃ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight or branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,aryl of 6 to 12 carbon atoms, or said aryl or said phenylalkylsubstituted on the aryl ring by 1 to 4 alkyl of 1 to 4 carbon atoms, and

E₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbonatoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbonatoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 12 carbon atomsor said aryl substituted by one or two alkyl of 1 to 4 carbon atoms or1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6to 16 carbon atoms,

or of the formula

where R and R₁₇ are defined as above, where R₁₇ is not hydrogen.

The present oxanilides are for example unsymmetrical and areperflouroalkyl substituted.

The present oxanilides are for example

The present oxanilides are for example

A further aspect of the invention is a composition comprising

(a) an organic polymer or recording material subject to the adverseeffects of ultraviolet light, and

(b) at least one oxanilde compound of formula (II).Yet another aspect of the invention is a process for the preparation ofan aryl substituted oxanilide of the formula

which process comprises adding together an arylboronic acid or ester ofthe formula

a halo- or tosyl-substituted oxalamide of the formula

and a transition-metal-catalyst, and

reacting the mixture for an appropriate time at an appropriatetemperature and pressure,

where

X is Cl, Br, I or tosyl,

R₆ and R₇ are independently hydrogen, straight or branched chain alkylof 1 to 12 carbon atoms, or together with the —OBO— group form a ring,

R is straight or branched chain alkoxy of 12 to 24 carbon atoms,

R₁₇ is perfluoroalkyl of 1 to 12 carbon atoms, cyano, nitro, —CO-G₃,—COOG₃, —CONHG₃,—CON(G₃)₂, E₃S—, E₃SO—, E₃SO₂—,

G₃ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight or branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,aryl of 6 to 12 carbon atoms, or said aryl or said phenylalkylsubstituted on the aryl ring by 1 to 4 alkyl of 1 to 4 carbon atoms, and

E₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbonatoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbonatoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 12 carbon atomsor said aryl substituted by one or two alkyl of 1 to 4 carbon atoms or1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6to 16 carbon atoms.

For example R₁₇ is ortho, meta, or para substituted C₁-C₁₂ perfluoalkyl.

Definitions and preferences for the substituents have already been givenand apply also for the process.

Preferably the catalyst is a palladium(II) catalyst and is present at alevel from about 0.01 to to about 10 mole percent based on thearylboronic acid or ester compound.

For example the process comprises adding triphenylphosphine as a ligand.

In another embodiment the process comprises adding1,1′-bis[2,4,8,10-tetrakis(1,1-dimethylethyl)-dibenzo[d,f][1,3,2]dioxa-phosphepin-6-yl]ferroceneas a ligand.

The present process may be anhydrous using dioxane as a solvent andpotassium fluoride as a base.

The present process may use 1-propanol or 2-propanol as a solvent.

The present process is for example carried out between about 10 andabout 100° C., for instance between about 50 and about 95° C., atatmospheric pressure.

Benzylidene Malonates

U.S. Pat. No. 3,706,701 specifies the use of methyl- and ethylbenzylidene malonates in which the substituent on the aromatic ring is asingle methyl ether in the 4-position. Ether groups in the 4-positionhave advantages as they provide for a beneficial red-shift of the UVabsorption and were shown to be more photochemically stable in celluloseacetate than where a methoxy group is present at the 2-position.

U.S. Pat. Nos. 4,260,732 and 4,404,257 also disclose benzylidenemalonates.

U.S. Pat. Nos. 5,705,545 and 6,262,153 B1 disclose benzylidene malonatessubstituted with groups which contain hindered amine moieties.

U.S. Pat. No. 5,882,624 discloses a cosmetic/dermatological compositionwhich includes a benzylidene malonate which can be substituted on thearyl ring by more than one alkoxy group. While generically the aryl canbe substituted by up to three alkoxy groups in unspecified positions,the 3,4, and 5-positions are preferred and the 3,4-bis and 3-4-5-trisalkoxy derivatives are exemplified.

An advantage of providing a benzylidene malonate with more than one arylsubstituent is that it allows one to shift the UV absorption spectra. Ithas been found that when more than one alkoxy group is present on thearyl ring, substitution at the 2-position is desirable for providing amaximum effect on UV absorption spectra. Furthermore, in contrast to themono substituted derivatives described in U.S. Pat. No. 3,706,701, ithas been found that in polyalkoxy derivatives substitution at the2-position provides equal or better photostability than found in similarderivatives bearing a 3-alkoxy substituent.

U.S. Pat. No. 3,244,668 discloses substituted cinnamates and relatedcompounds with a variety of substituents.

Accordingly, benzylidene malonates of this invention are of formula(III)

where

R₂₁, R₂₂ and R₂₃ are independently hydrogen, straight or branched chainalkyl of 1 to 24 carbon atoms, straight or branched chain alkoxy 1 to 24carbon atoms, or said alkyl or alkoxy substituted by one or more —OH,—COOE₁₁, —OCOE₁₁, —OE₄, —NHCOE₁₁ or —NE₇E₈ groups or mixtures thereof,where E₄ is straight or branched chain alkyl of 1 to 24 carbon atoms orstraight or branched chain alkenyl of 2 to 18 carbon atoms;

where at least two of the R₂₁, R₂₂ and R₂₃ groups are alkoxy orsubstituted alkoxy;

E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms,C₆-C₁₄aryl, C₇-C₁₅aralkyl, straight or branched chain alkenyl of 2 to 18carbon atoms, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl, or E₇and E₈ together with the N atom are a pyrrolidine, piperidine,piperazine or morpholine ring,

E₁₁ is hydrogen, straight or branched chain C₁-C₂₄alkyl, saidC₁-C₂₄alkyl substituted by 1 to 4 hydroxyl groups, C₅-C₁₂cycloalkyl orstraight or branched chain C₃-C₁₈alkenyl;

or E₁₁ is a group

where

E₅₀ is hydrogen, oxyl, straight or branched chain alkyl of 1 to 24carbon atoms, straight or branched chain alkenyl of 3 to 24 carbonatoms, benzyl, acetyl, —CH₂CH(OH)-E₅₁, —OE₅₂, —OE₅₃(OH)_(b),

E₅₁ is hydrogen, methyl, ethyl or phenyl,

E₅₂ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, straight or branched chainalkenyl of 3 to 24 carbon atoms, cycloalkenyl of 5 to 12 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, a radical of a saturated orunsaturated bicyclic or tricyclic hydrocarbon of 7 to 15 carbon atoms,aryl of 6 to 12 carbon atoms or said aryl substituted by one to threealkyl of 1 to 4 carbon atoms;

E₅₃ is a straight or branched chain alkyl of 1 to 24 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, cycloalkenyl of 5 to 12 carbonatoms, straight or branched chain alkenyl of 3 to 24 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 12 carbon atoms orsaid aryl substituted by one to three alkyl of 1 to 4 carbon atoms;

b is 1, 2 or 3 with the restriction that b cannot exceed the number ofcarbon atoms in E₅₃, and if b is 2 or 3, each hydroxyl group is attachedto a different carbon atom of E₅₃; and

z is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms,phenyl or phenyl substituted by 1 to 4 straight or branched chain alkylof 1 to 4 carbon atoms, straight or branched chain alkoxy of 1 to 12carbon atoms, or said alkyl or alkoxy substituted by one or more —OH,—COOE₁₁, —OCOE₁₁, —OE₄, —NHCOE₁₁ or

—NE₇E₈ groups or mixtures thereof, where E₄ is straight or branchedchain alkyl of 1 to 24 carbon atoms or straight or branched chainalkenyl of 2 to 18 carbon atoms.

For example, at least two of R₂₁, R₂₂ and R₂₃ are alkoxy.

For example z is hydrogen.

For example E₁₁ is alkyl.

R₂₁, R₂₂ and R₂₃ are for example hydrogen, methoxy or methyl, forexample where: R₂₁ R₂₂ R₂₃ H OCH₃ OCH₃ OCH₃ H OCH₃ OCH₃ OCH₃ H OCH₃ OCH₃OCH₃ CH₃ OCH₃ OCH₃ OCH₃ CH₃ OCH₃ OCH₃ OCH₃ CH₃R₂₁, R₂₂ and R₂₃ are for example alkoxy alkoxy.A further aspect of the invention is a composition comprising

(a) an organic polymer or recording material subject to the adverseeffects of ultraviolet light, and

(b) at least one benzylidene malonate of formula (III).

Quinazolines

The novel quinazolines are of formula (IV)

where

R is hydrogen, halogen, straight or branched chain thioether of 1 to 24carbon atoms, straight or branched chain alkoxy of 1 to 24 carbon atoms,cycloalkoxy of 5 to 12 carbon atoms, phenoxy or phenoxy substituted by 1to 4 alkyl of 1 to 4 carbon atoms, phenylalkoxy of 7 to 15 carbon atoms,perfluoroalkoxy of 1 to 24 carbon atoms, cyano, perfluoroalkyl of 1 to12 carbon atoms, —CO-G₃, —COOG₃, —CONHG₃, —CON(G₃)₂, E₃S—, E₃SO—,E₃SO₂—, nitro, —P(O)(C₆H₅)₂, —P(O)(OG₃)₂,

G₃ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight or branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,aryl of 6 to 12 carbon atoms, or said aryl or said phenylalkylsubstituted on the aryl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,

or R is hydroxy, straight or branched chain alkyl of 1 to 24 carbonatoms, straight or branched chain alkenyl of 2 to 24 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,aryl of 6 to 12 carbon atoms, or said aryl or said phenylalkylsubstituted on the aryl ring by 1 to 4 alkyl of 1 to 4 carbon atoms;

or R is said alkyl of 1 to 24 carbon atoms or said alkoxy of 1 to 24carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by oneor more —OH, —COOE₁₁, —OCOE₁₁, —OE₄, —NCO, —NHCOE₁₁, —NE₇E₈ or

groups or mixtures thereof, where E₄ is straight or branched chain alkylof 1 to 24 carbon atoms or straight or branched chain alkenyl of 2 to 18carbon atoms; or said alkyl or said alkenyl interrupted by one or more—O—, —NH— or —NE₄- groups or mixtures thereof and which can beunsubstituted or substituted by one or more —OH, —OE₄, —NH₂ or —COOE₁₁or

groups or mixtures thereof,

or R is a group of formula

where

E₂₇ and E₂₈ are independently alkyl of 1 to 18 carbon atoms, orcycloalkyl of 5 to 12 carbon atoms;

E₂₂, E₂₃, E₂₄, E₂₅ and E₂₆ are independently hydrogen, halogen, straightor branched alkyl of 1 to 18 carbon atoms, alkenyl of 2 to 18 carbonatoms, said alkyl or said alkenyl substituted by one or more halogen,—OCOE₁₁, —OE₄, —NCO, —NHCOE₁₁ or —NE₇E₈, or mixtures thereof, where E₄is straight or branched chain alkyl of 1 to 24 carbon atoms or straightor branched chain alkenyl of 2 to 18 carbon atoms; or said alkyl or saidalkenyl interrupted by one or more —O—, —NH— or —NE₄- groups or mixturesthereof and which can be unsubstituted or substituted by one or more—OH, or —NH₂, or mixtures thereof; or

E₂₂, E₂₃, E₂₄, E₂₅ and E₂₆ are independently phenyl, phenylalkyl of 7 to15 carbon atoms, —OH, —OCOE₁₁, —OE₂₉, —NCO, —NHCOE₁₁ or —NE₇E₈, cyano,nitro, perfluoroalkyl of 1 to 12 carbon atoms, —COG₃, —COOG₃, —CON(G₃)₂,—CONHG₃, E₃S—, E₃SO—, E₃SO₂—, —P(O)(C₆H₅)₂,

—P(O))OG₃)₂, —SO₂—X₁-E₂₉;

X₁ is —O—, —NH— or —NE₄-;

E₂₉ is straight or branched chain alkyl of 1 to 24 carbon atoms,straight or branched chain alkenyl of 2 to 18 carbon atoms, said alkylor said alkenyl substituted by one or more —OH, —OCOE₁₁, —OE₄, —NCO,—NHCOE₁₁, —NE₇E₈, phthalimido,

or mixtures thereof, where E₄ is straight or branched chain alkyl of 1to 24 carbon atoms or alkenyl of 2 to 18 carbon atoms; or said alkyl orsaid alkenyl interrupted by one or more —O—, —NH— or —NE₄- groups ormixtures thereof and which can be unsubstituted or substituted by one ormore —OH, or —NH₂, or mixtures thereof; or E₂₉ is aryl of 6 to 12 carbonatoms or phenylalkyl of 7 to 15 carbon atoms, or said aryl or saidphenylalkyl substituted by one to three alkyl groups of 1 to 4 carbonatoms;

E₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbonatoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbonatoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 12 carbon atomsor said aryl substituted by one or two alkyl of 1 to 4 carbon atoms or1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6to 16 carbon atoms,

E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms,straight or branched chain C₃-C₁₈alkyl which is interrupted by —O—, —S—or —NE₁₁-, straight or branched chain alkenyl of 2 to 18 carbon atoms,C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl, or E₇ and E₈together with the N atom are a pyrrolidine, piperidine, piperazine ormorpholine ring, or

E₁₁ is hydrogen, straight or branched chain C₁-C₂₄alkyl,C₅-C₁₂cycloalkyl, straight or branched chain C₃-C₁₈alkenyl, C₆-C₁₄arylor C₇-C₁₅aralkyl; or said alkyl substituted by one or more

groups,

E₅₀ is hydrogen, oxyl, straight or branched chain alkyl of 1 to 24carbon atoms, straight or branched chain alkenyl of 3 to 24 carbonatoms, benzyl, acetyl, —CH₂CH(OH)-E₅₁, —OE₅₂, —OE₅₃(OH)_(b),

E₅₁ is hydrogen, methyl, ethyl or phenyl,

E₅₂ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, straight or branched chainalkenyl of 3 to 24 carbon atoms, cycloalkenyl of 5 to 12 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, a radical of a saturated orunsaturated bicyclic or tricyclic hydrocarbon of 7 to 15 carbon atoms,aryl of 6 to 12 carbon atoms or said aryl substituted by one to threealkyl of 1 to 4 carbon atoms; or a group of formula

E₅₃ is a straight or branched chain alkyl of 1 to 24 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, cycloalkenyl of 5 to 12 carbonatoms, straight or branched chain alkenyl of 3 to 24 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 12 carbon atoms orsaid aryl substituted by one to three alkyl of 1 to 4 carbon atoms;

b is 1, 2 or 3 with the restriction that b cannot exceed the number ofcarbon atoms in E₅₃, and if b is 2 or 3, each hydroxyl group is attachedto a different carbon atom of E₅₃; and

E₅₄ to E₅₈ are independently hydrogen, halogen, nitro, cyano, alkyl of 1to 18 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 12carbon atoms, hydroxyl, carboxyl, alkylthio of 1 to 18 carbon atoms,straight or branched chain alkoxy of 1 to 18 carbon atoms, cycloalkoxyof 5 to 12 carbon atoms, phenylalkoxy of 7 to 15 carbon atoms, aryloxyof 6 to 10 carbon atoms, alkylcarbonyloxy of 2 to 18 carbon atoms,alkylsulfonyl of 1 to 18 carbon atoms, arylsulfonyl of 6 to 15 carbonatoms, sulfo or phosphono, or any two vicinal substituents connectedtogether to form a mono- or polycyclic ring.

Quinazolines of the present invention are for example

where

E₂₃ is phenylalkyl of 7 to 15 carbon atoms and

E₂₅ is straight or branched chain alkyl of 1 to 18 carbon atoms.

For example, the present quinazolines are of the formula

where

E₂₅ is straight or branched chain alkyl of 1 to 18 carbon atoms and

E₂₄ is straight or branched chain alkoxy of 1 to 24 carbon atoms.

For example of the formula

where

E₂₅ is straight or branched chain alkyl of 1 to 18 carbon atoms,

E₂₄ is straight or branched chain alkoxy of 1 to 24 carbon atoms and

R is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms,aryl of 6 to 12 carbon atoms or aryl substituted by 1 to 4 alkyl of 1 to4 carbon atoms, straight or branched chain alkoxy of 1 to 24 carbonatoms, halogen, cyano, perfluoroalkyl of 1 to 12 carbon atoms, E₃S—,E₃SO—, E₃SO₂— or biphenyl.

For example, the present quinazolines are

where

E₂₄ is straight or branched chain alkoxy of 1 to 24 carbon atoms and

R is hydrogen, CH₃, phenyl, —OCH₃, Cl, —CN, —CF₃, —SPh, —SO₂Ph orbiphenyl.

Also an aspect of the invention is a composition comprising

(a) an organic polymer or recording material subject to the adverseeffects of ultraviolet light, and

(b) at least one quinazoline compound of formula (IV).

Benzotriazoles

Phenolic benzotriazole, that is ortho-hydroxyphenyl-2H-benzotriazole,ultraviolet light absorbers have long been known and have achievedcommercial success as stabilizers for polymer substrates, for example inthermoplastic articles and coating compositions.

Non-phenolic benzotriazole ultraviolet light absorbers (UVA's) areunknown. Non-phenolic benzotriazole additives may provide certainadvantages or properties not achievable with phenolic UVA's. It has beendiscovered that certain non-phenolic compounds of the benzotriazoleclasses are suitable as ultraviolet light absorbers.

The novel benzotriazoles of the present invention are represented byformula (V)

in which

G₁ and G₂ are independently hydrogen, halogen, straight or branchedchain thioether of 1 to 24 carbon atoms, straight or branched chainalkoxy of 1 to 24 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms,phenoxy or phenoxy substituted by 1 to 4 alkyl of 1 to 4 carbon atoms,phenylalkoxy of 7 to 15 carbon atoms, perfluoroalkoxy of 1 to 24 carbonatoms, cyano, perfluoroalkyl of 1 to 12 carbon atoms, —CO-G₃, —COOG₃,—CONHG₃, —CON(G₃)₂, E₃S—, E₃SO—, E₃SO₂—, nitro, —P(O)(C₆H₅)₂,—P(O)(OG₃)₂,

G₃ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight or branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,aryl of 6 to 12 carbon atoms, or said aryl or said phenylalkylsubstituted on the aryl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,

R₂, R₃ and R₄ are independently hydrogen, hydroxy, straight or branchedchain alkyl of 1 to 24 carbon atoms, straight or branched chain alkoxyof 1 to 24 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms, phenoxy orphenoxy substituted by 1 to 4 alkyl of 1 to 4 carbon atoms, phenylalkoxyof 7 to 15 carbon atoms, straight or branched chain alkenyl of 2 to 24carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15carbon atoms, aryl of 6 to 12 carbon atoms, or said aryl or saidphenylalkyl substituted on the aryl ring by 1 to 4 alkyl of 1 to 4carbon atoms;

or R₂, R₃ and R₄ are independently said alkyl of 1 to 24 carbon atoms orsaid alkenyl of 2 to 18 carbon atoms substituted by one or more —OH,—COOE₁₁, —OCOE₁₁, —OE₄, —NCO, —NHCOE₁₁, —NE₇E₈ or

groups or mixtures thereof, where E₄ is straight or branched chain alkylof 1 to 24 carbon atoms or straight or branched chain alkenyl of 2 to 18carbon atoms; or said alkyl or said alkenyl interrupted by one or more—O—, —NH— or —NE₄- groups or mixtures thereof and which can beunsubstituted or substituted by one or more —OH, —NH₂ or —COOE₁₁ or

groups or mixtures thereof,

or R₁, R₂ and R₄ are independently a group of formula

where

E₂₇ and E₂₈ are independently alkyl of 1 to 18 carbon atoms, orcycloalkyl of 5 to 12 carbon atoms;

E₂₂, E₂₃, E₂₄, E₂₅ and E₂₆ are independently hydrogen, halogen, straightor branched alkyl of 1 to 18 carbon atoms, alkenyl of 2 to 18 carbonatoms, said alkyl or said alkenyl substituted by one or more halogen,—OCOE₁₁, —OE₄, —NCO, —NHCOE₁₁ or —NE₇E₈, or mixtures thereof, where E₄is straight or branched chain alkyl of 1 to 24 carbon atoms or straightor branched chain alkenyl of 2 to 18 carbon atoms; or said alkyl or saidalkenyl interrupted by one or more —O—, —NH— or —NE₄- groups or mixturesthereof and which can be unsubstituted or substituted by one or more—OH, or —NH₂, or mixtures thereof; or

E₂₂, E₂₃, E₂₄, E₂₅ and E₂₆ are independently phenyl, phenylalkyl of 7 to15 carbon atoms, —OH, —OCOE₁₁, —OE₂₉, —NCO, —NHCOE₁₁ or —NE₇E₈, cyano,nitro, perfluoroalkyl of 1 to 12 carbon atoms, —COG₃, —COOG₃, —CON(G₃)₂,—CONHG₃, E₃S—, E₃SO—, E₃SO₂—, —P(O)(C₆H₅)₂,

—P(O))OG₃)₂, —SO₂—X₁-E₂₉;

X₁ is —O—, —NH— or —NE₄-;

E₂₉ is straight or branched chain alkyl of 1 to 24 carbon atoms,straight or branched chain alkenyl of 2 to 18 carbon atoms, said alkylor said alkenyl substituted by one or more —OH, —OCOE₁₁, —OE₄, —NCO,—NHCOE₁₁, —NE₇E₈, phthalimido,

or mixtures thereof, where E₄ is straight or branched chain alkyl of 1to 24 carbon atoms or alkenyl of 2 to 18 carbon atoms; or said alkyl orsaid alkenyl interrupted by one or more —O—, —NH— or —NE₄- groups ormixtures thereof and which can be unsubstituted or substituted by one ormore —OH, or —NH₂, or mixtures thereof; or E₂₉ is aryl of 6 to 12 carbonatoms or phenylalkyl of 7 to 15 carbon atoms, or said aryl or saidphenylalkyl substituted by one to three alkyl groups of 1 to 4 carbonatoms;

E₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbonatoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbonatoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 12 carbon atomsor said aryl substituted by one or two alkyl of 1 to 4 carbon atoms or1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6to 16 carbon atoms,

E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms,straight or branched chain C₃-C₁₈alkyl which is interrupted by —O—, —S—or —NE₁₁-, straight or branched chain alkenyl of 2 to 18 carbon atoms,C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl, or E₇ and E₈together with the N atom are a pyrrolidine, piperidine, piperazine ormorpholine ring, or

E₁₁ is hydrogen, straight or branched chain C₁-C₂₄alkyl,C₅-C₁₂cycloalkyl, straight or branched chain C₂-C₁₈alkenyl, C₆-C₁₄arylor C₇-C₁₅aralkyl; or said alkyl substituted by one or more

groups,

E₅₀ is hydrogen, oxyl, straight or branched chain alkyl of 1 to 24carbon atoms, straight or branched chain alkenyl of 3 to 24 carbonatoms, benzyl, acetyl, —CH₂CH(OH)-E₅₁, —OE₅₂, —OE₅₃(OH)_(b),

E₅₁ is hydrogen, methyl, ethyl or phenyl,

E₅₂ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, straight or branched chainalkenyl of 3 to 24 carbon atoms, cycloalkenyl of 5 to 12 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, a radical of a saturated orunsaturated bicyclic or tricyclic hydrocarbon of 7 to 15 carbon atoms,aryl of 6 to 12 carbon atoms or said aryl substituted by one to threealkyl of 1 to 4 carbon atoms; or a group of formula

E₅₃ is a straight or branched chain alkyl of 1 to 24 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, cycloalkenyl of 5 to 12 carbonatoms, straight or branched chain alkenyl of 3 to 24 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 12 carbon atoms orsaid aryl substituted by one to three alkyl of 1 to 4 carbon atoms;

b is 1, 2 or 3 with the restriction that b cannot exceed the number ofcarbon atoms in E₅₃, and if b is 2 or 3, each hydroxyl group is attachedto a different carbon atom of E₅₃;

E₅₄ to E₅₈ are independently hydrogen, halogen, nitro, cyano, alkyl of 1to 18 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 12carbon atoms, hydroxyl, carboxyl, alkylthio of 1 to 18 carbon atoms,straight or branched chain alkoxy of 1 to 18 carbon atoms, cycloalkoxyof 5 to 12 carbon atoms, phenylalkoxy of 7 to 15 carbon atoms, aryloxyof 6 to 10 carbon atoms, alkylcarbonyloxy of 2 to 18 carbon atoms,alkylsulfonyl of 1 to 18 carbon atoms, arylsulfonyl of 6 to 15 carbonatoms, sulfo or phosphono, or any two vicinal substituents connectedtogether to form a mono- or polycyclic ring;

R₁ and R₅ are independently as defined for R₂, R₃ and R₄, with theproviso that neither may be hydroxy;

or R₁ and R₂ together may form a 5 to 7 membered ring which may beinterrupted by —O—, —NG₃- or —S—, which ring may be further substitutedby straight or branched chain alkyl of 1-12 carbon atoms, aryl of 6 to12 carbon atoms or phenylalkyl of 7 to 15 carbon atoms.

For example, the present benzotriazoles are of the formula

where

G₁ is hydrogen or perfluoroalkyl of 1 to 12 carbon atoms,

R₂ is hydrogen or straight or branched chain alkyl of 1 to 24 carbonatoms,

R₃ is hydrogen, hydroxy or straight or branched chain alkoxy of 1 to 24carbon atoms,

R₄ is hydrogen or straight or branched chain alkyl of 1 to 24 carbonatoms,

R₅ is hydrogen or straight or branched chain alkyl of 1 to 24 carbonatoms and

R₁ is straight or branched chain alkyl of 1 to 24 carbon atoms orstraight or branched chain alkoxy of 1 to 24 carbon atoms.

For example, the present benzotriazole compounds are of the formula

where

G₁ is hydrogen or —CF₃,

R₂ is hydrogen or —CH₃,

R₃ is hydrogen, hydroxy or —OCH₃,

R₄ is hydrogen, tert-butyl or —CH₃,

R₅ is hydrogen or —CH₃ and

R₁ is —CH₃ or —OCH₃.

Specific examples of benzotriazoles of the present invention are

Present benzotriazoles are for example

where G₁ R₂ R₃ R₄ R₅ R₁ H H OH t-butyl H CH₃ H H OCH₃ t-butyl H CH₃ CF₃CH₃ OH H H CH₃ CF₃ CH₃ OCH₃ H H CH₃ H CH₃ OH H H CH₃ H CH₃ OCH₃ H H CH₃H H H CH₃ CH₃ OCH₃ CF₃ H H CH₃ CH₃ OCH₃

For example, present benzotriazoles have substituents (groups other thanhydrogen) in both the R₁ and R₅ positions of the phenyl ring, the ortho,ortho positions.

Yet another aspect of the invention is a composition comprising

(a) an organic polymer or recording material subject to the adverseeffects of ultraviolet light, and

(b) at least one benzotriazole compound of formula (V).

In the present compounds:

Straight or branched chain alkyl is for example methyl, ethyl, propyl,isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl,n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl,1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl,1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl,1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, icosyl ordocosyl.

Cycloalkyl or susbstituted cycloalkyl is for example cyclopentyl,methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl,dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl,cycloheptyl or cyclooctyl.

Aryl is for example phenyl, biphenyl and napthyl.

Aryl substituted by alkyl is for example o-, m- or p-methylphenyl,2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl,2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl,2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl or2,6-diethylphenyl.

Phenylalkyl is for example, benzyl, α-methylbenzyl, α,α-dimethylbenzylor 2-phenylethyl. Cumyl is α,α-dimethylbenzyl or α-cumyl.

Phenylalkyl or substituted phenylalkyl is for example 2-methylbenzyl,3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzylor 4-tert-butylbenzyl.

Straight or branched chain alkoxy is for example methoxy, ethoxy,propoxy, isopropoxy, n-butoxy, isobutoxy, pentyloxy, isopentyloxy,hexyloxy, heptyloxy, octyloxy, decyloxy, tetradecyloxy, hexadecyloxy oroctadecyloxy.

Cycloalkoxy is for example, cyclopentyloxy, methylcyclopentyloxy,dimethylcyclopentyloxy, cyclohexyloxy, methylcyclohexyloxy,dimethylcyclohexyloxy, trimethylcyclohexyloxy, tert-butylcyclohexyloxy,cycloheptyloxy or cyclooctyloxy.

Phenoxy substituted by one to three alkyl is for example o-, m- orp-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy,2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy,3,5-dimethylphenoxy, 2-methyl-6-ethylphenoxy, 4-tert-butylphenoxy,2-ethylphenoxy or 2,6-diethylphenoxy.

Phenylalkoxy of 7 to 15 carbon atoms is for example, benzyloxy,α-methylbenzyloxy, α,α-dimethylbenzyloxy or 2-phenylethoxy.

Straight or branched chain alkylthio (thioether) is for examplemethylthio, ethylthio, propylthio, isopropylthio, n-butylthio,isobutylthio, pentylthio, isopentylthio, hexylthio, heptylthio,octylthio, decylthio, tetradecylthio, hexadecylthio or octadecylthio.

The present invention also relates to compositions stabilized againstthe deleterious effects of ultraviolet radiation which comprise thepresent novel ultraviolet light absorbers.

Accordingly, the present invention is also directed to a compositioncomprising

(a) an organic polymer or recording material subject to the adverseeffects of ultraviolet light, and

(b) at least one compound selected from the present benzoxazinone,oxanilide, benzylidene malonate, quinazoline and benzotriazolecompounds.

The polymer substrates of component (a) are natural or syntheticpolymers or copolymers. The substrates of component (a) are for examplesynthetic polymers, in particular thermoplastic polymers such aspolyamides and polyolefins. Polyolefins are for instance polypropyleneor polyethylene.

Suitable polymer substrates of component (a) are for example:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybutadiene, poly-4-methylpent-1-ene,polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymersof cycloolefins, for instance of cyclopentene or norbornene,polyethylene (which optionally can be crosslinked), for example highdensity polyethylene (HDPE), high density and high molecular weightpolyethylene (HDPE-HMW), high density and ultrahigh molecular weightpolyethylene (HDPE-UHMW), medium density polyethylene (MDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

a) radical polymerization (normally under high pressure and at elevatedtemperature).

b) catalytic polymerization using a catalyst that normally contains oneor more than one metal of groups IVb, Vb, VIb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerizationmedium. The catalysts can be used by themselves in the polymerization orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers(e.g. ethylene/norbornene like COC), ethylene/1-olefins copolymers,where the 1-olefin is generated in-situ; propylene/butadiene copolymers,isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acidcopolymers and their salts (ionomers) as well as terpolymers of ethylenewith propylene and a diene such as hexadiene, dicyclopentadiene orethylidene-norbornene; and mixtures of such copolymers with one anotherand with polymers mentioned in 1) above, for examplepolypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetatecopolymers (EVA), LDPE/ethyleneacrylic acid copolymers (EAA), LLDPE/EVA,LLDPE/EAA and alternating or random polyalkylene/carbon monoxidecopolymers and mixtures thereof with other polymers, for examplepolyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

Homopolymers and copolymers from 1.)-4.) may have any stereostructureincluding syndiotactic, isotactic, hemi-isotactic or atactic; whereatactic polymers are preferred. Stereoblock polymers are also included.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Aromatic homopolymers and copolymers derived from vinyl aromaticmonomers including styrene, α-methylstyrene, all isomers of vinyltoluene, especially p-vinyltoluene, all isomers of ethyl styrene, propylstyrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, andmixtures thereof. Homopolymers and copolymers may have anystereostructure including syndiotactic, isotactic, hemi-isotactic oratactic; where atactic polymers are preferred. Stereoblock polymers arealso included.

6a. Copolymers including aforementioned vinyl aromatic monomers andcomonomers selected from ethylene, propylene, dienes, nitriles, acids,maleic anhydrides, maleimides, vinyl acetate and vinyl chloride oracrylic derivatives and mixtures thereof, for example styrene/butadiene,styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkylmethacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkylmethacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methylacrylate; mixtures of high impact strength of styrene copolymers andanother polymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

6b. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6.), especially includingpolycyclohexylethylene (PCHE) prepared by hydrogenating atacticpolystyrene, often referred to as polyvinylcyclohexane (PVCH).

6c. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6a.).

Homopolymers and copolymers may have any stereostructure includingsyndiotactic, isotactic, hemi-isotactic or atactic; where atacticpolymers are preferred. Stereoblock polymers are also included.

7. Graft copolymers of vinyl aromatic monomers such as styrene orα-methylstyrene, for example styrene on polybutadiene, styrene onpolybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styreneand acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,acrylonitrile and methyl methacrylate on polybutadiene; styrene andmaleic anhydride on polybutadiene; styrene, acrylonitrile and maleicanhydride or maleimide on polybutadiene; styrene and maleimide onpolybutadiene; styrene and alkyl acrylates or methacrylates onpolybutadiene; styrene and acrylonitrile on ethylene/propylene/dieneterpolymers; styrene and acrylonitrile on polyalkyl acrylates orpolyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadienecopolymers, as well as mixtures thereof with the copolymers listed under6), for example the copolymer mixtures known as ABS, SAN, MBS, ASA orAES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate(PAN) and polyhydroxybenzoates, as well as block copolyether estersderived from hydroxyl-terminated polyethers; and also polyestersmodified with polycarbonates or MBS. Polyesters and polyester copolymersas defined in U.S. Pat. No. 5,807,932 (column 2, line 53), incorporatedherein by reference.

19. Polycarbonates and polyester carbonates.

20. Polyketones.

21. Polysulfones, polyether sulfones and polyether ketones.

22. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

23. Drying and non-drying alkyd resins.

24. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

25. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

26. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenol F, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.

28. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

29. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

30. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

31. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

32. Polysiloxanes such as the soft, hydrophilic polysiloxanes described,for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

33. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

34. Radiation curable compositions containing ethylenically unsaturatedmonomers or oligomers and a polyunsaturated aliphatic oligomer.

35. Epoxymelamine resins such as light-stable epoxy resins crosslinkedby an epoxy functional coetherified high solids melamine resin such asLSE-4103 (Monsanto).

Materials that are stabilized according to the instant invention includerecording materials such as photographic reproductions or reprographicmaterials. The novel recording materials also include, for example,pressure-sensitive copying systems, microcapsule photocopier systems,heat-sensitive copier systems, photographic material and ink-jetprinting.

Materials stabilized according to the present invention includethermoplastic molded articles, fibers and films.

Materials stabilized according to the present invention includeautomotive coatings.

Compositions stabilized according to the present invention also includephotographic materials, polyolefin articles exposed to chlorine,gamma-irradiated polyolefins, woven or nonwoven polyolefin fibers orfabrics, polyolefin hollow article prepared by the rotomolding process,recycled plastics, coextruded films over PVC, PC or ABS, multilayerpolymer structures, and radiation-cured inks or coatings.

Further in addition to component (b), the present stabilizedcompositions may comprise other traditional additives selected from, forexample, other antioxidants, other UV absorbers, other hindered amines,other phosphites or phosphonites, benzofuran-2-ones, thiosynergists,polyamide stabilizers, metal stearates, nucleating agents, fillers,reinforcing agents, lubricants, emulsifiers, dyes, pigments, opticalbrighteners, flame retardants, antistatic agents, blowing agents and thelike, such as the materials listed below, or mixtures thereof. Theseoptional further additives are present from about 0.01 to about 10% byweight; for example from about 0.025 to about 5% by weight, for instancefrom about 0.1 to about 3% by weight, based on the total weight of thecomposition.

These other traditional additives are selected from, for example:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tertbutyl-4-methoxymethylphenol, nonylphenols which are linear orbranched in the side chains, for example, 2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1-methylundec-1-yl)phenol,2,4-dimethyl-6-(1-methylheptadec-1-yl)phenol,2,4-dimethyl-6-(1-methyltridec-1-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′tert-butyl-2-hydroxy-5-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. Benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide,3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester,bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate,1,3,5-tris-(3,5-di-tertbutyl-4-hydroxybenzyl) isocyanurate,1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester and3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,calcium-salt.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tertbutyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxy-lauric acid anilide,4-hydroxystearic acid anilide,2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine andoctyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.

1.13. Esters of β-(3.5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15. Esters of β-(3.5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3.5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3.5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tertbutyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1 supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenlenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyidiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyl-diphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octyl-phenothiazines, N-allylphenothiazin,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV Absorbers and Light Stabilizers

2.1. 2-(2-Hydroxyphenyl)-2H-benzotriazoles, for example known commercialhydroxyphenyl-2H-benzotriazoles and benzotriazoles as disclosed in,United States Patent Nos. 3,004,896; 3,055,896; 3,072,585; 3,074,910;3,189,615; 3,218,332; 3,230,194; 4,127,586; 4,226,763; 4,275,004;4,278,589; 4,315,848; 4,347,180; 4,383,863; 4,675,352; 4,681,905,4,853,471; 5,268,450; 5,278,314; 5,280,124; 5,319,091; 5,410,071;5,436,349; 5,516,914; 5,554,760; 5,563,242; 5,574,166; 5,607,987,5,977,219 and 6,166,218 such as2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole,5-chloro-2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,5-chloro-2-(3-t-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-sec-butyl-5-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole,2-(3,5-di-t-amyl-2-hydroxyphenyl)-2H-benzotriazole,2-(3,5-bis-α-cumyl-2-hydroxyphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-((ω-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,phenyl)-2H-benzotriazole,2-(3-dodecyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonyl)ethylphenyl)-2H-benzotriazole,dodecylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)-carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-benzotriazole,2-(3-t-butyl-5-(2-(2-ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl-2H-benzotriazole,2,2′-methylene-bis(4-t-octyl-(6-2H-benzotriazol-2-yl)phenol),2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,2-(2-hydroxy-3-t-octyl-5-α-cumylphenyl)-2H-benzotriazole,5-fluoro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-octylphenyl)-2H-benzotriazole,methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyhydrocinnamate,5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-t-butylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-butylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole and5-phenylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, as forexample 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tertbutyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates and malonates, for example, α-cyano-β,β-diphenylacrylicacid ethyl ester or isooctyl ester, α-carbomethoxy-cinnamic acid methylester, α-cyano-β-methyl-β-methoxy-cinnamic acid methyl ester or butylester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N—(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline, Sanduvor® PR25,dimethyl p-methoxybenzylidenemalonate (CAS# 7443-25-6), and Sanduvor®PR31, di-(1,2,2,6,6-pentamethylpiperidin-4-yl)p-methoxybenzylidenemalonate (CAS #147783-69-5).

2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically hindered amine stabilizers, for example4-hydroxy-2,2,6,6-tetramethylpiperidine,1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl) succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear or cycliccondensates ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane and epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxy-methylene-malonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,reaction product of maleic acid anhydride-α-olefin-copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

The sterically hindered amine may also be one of the compounds describedU.S. Pat. No. 5,980,783, the relevant parts of which are herebyincorporated by reference, that is compounds of component I-a), I-b),I-c), I-d), I-e), I-f), I-g), I-h), I-i), I-j), I-k) or I-I), inparticular the light stabilizer 1-a-1, 1-a-2, 1-b-1, 1-c-1, 1-c-2,1-d-1, 1-d-2, 1-d-3, 1-e-1, 1-f-1, 1-g-1, 1-g-2 or 1-k-1 listed oncolumns 64-72 of said U.S. Pat. No. 5,980,783.

The sterically hindered amine may also be one of the compounds describedin EP 782994, for example compounds as described in claims 10 or 38 orin Examples 1-12 or D-1 to D-5 therein.

2.7. Sterically hindered amines substituted on the N-atom by ahydroxy-substituted alkoxy group, for example compounds such as1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine,the reaction product of 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidinewith a carbon radical from t-amylalcohol,1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine,1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)adipate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)succinate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)glutarate and2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethylamino)-s-triazine.

2.8. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.9. Tris-aryl-o-hydroxyphenyl-s-triazines, for example known commercialtris-aryl-o-hydroxyphenyl-s-triazines and triazines as disclosed in, WO96/28431, EP 434608, EP 941989, GB 2,317,893, U.S. Pat. Nos. 3,843,371;4,619,956; 4,740,542; 5,096,489; 5,106,891; 5,298,067; 5,300,414;5,354,794; 5,461,151; 5,476,937; 5,489,503; 5,543,518; 5,556,973;5,597,854; 5,681,955; 5,726,309; 5,942,626; 5,959,008; 5,998,116 and6,013,704, and U.S. application Ser. No. 09/383,163, for example4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine,Cyasorb® 1164, Cytec Corp,4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine,2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl)-s-triazine,2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-α-cumylphenyl]-s-triazine(* denotes a mixture of octyloxy, nonyloxy and decyloxy groups),methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)phenyl]-s-triazine},methylene bridged dimer mixture bridged in the 3:5′, 5:5′ and 3:3′positions in a 5:4:1 ratio,2,4,6-tris(2-hydroxy-4-isooctyloxycarbonyliso-propylideneoxyphenyl)-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-α-cumylphenyl)-s-triazine,2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,mixture of4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2-hydroxypropoxy)-phenyl)-s-triazineand4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-tridecyloxy-2-hydroxypropoxy)-phenyl)-s-triazine,Tinuvin® 400, Ciba Specialty Chemicals Corp.,4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)phenyl)-s-triazineand 4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl) hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-dibenzo[d,f][1,3,2]dioxaphosphepin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g][1,3,2]dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,2,2′,2″-nitrilo[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite.

Especially preferred are the following phosphites:

Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos®168, Ciba SpecialtyChemicals Corp.), tris(nonylphenyl) phosphite,

5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N-methyl-N-octadecylhydroxylamineand the N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

6. Nitrones, for example N-benzyl-α-phenylnitrone,N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone,N-lauryl-α-undecylnitrone, N-tetradecyl-α-tridcylnitrone,N-hexadecyl-α-pentadecylnitrone, N-octadecyl-α-heptadecylnitrone,N-hexadecyl-α-heptadecylnitrone, N-ocatadecyl-α-pentadecylnitrone,N-heptadecyl-α-heptadecylnitrone, N-octadecyl-α-hexadecylnitrone,N-methyl-α-heptadecylnitrone and the nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Amine oxides, for example amine oxide derivatives as disclosed inU.S. Pat. Nos. 5,844,029 and 5,880,191, didecyl methyl amine oxide,tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amineoxide.

8. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052, 5,252,643;DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]-phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxy-phenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, Irganox®HP-136, Ciba Specialty Chemicals Corp., and3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

9. Thiosynergists, for example dilauryl thiodipropionate or distearylthiodipropionate.

10. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

11. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese, forexample Cul.

12. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example, calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zincpyrocatecholate.

13. Nucleating agents, for example inorganic substances such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds such as ioniccopolymers (ionomers).

14. Fillers and reinforcing agents, for example calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

15. Dispersing Agents, such as polyethylene oxide waxes or mineral oil.

16. Other additives, for example plasticizers, lubricants, emulsifiers,pigments, dyes, optical brighteners, rheology additives, catalysts,flow-control agents, slip agents, crosslinking agents, crosslinkingboosters, halogen scavengers, smoke inhibitors, flameproofing agents,antistatic agents, clarifiers such as substituted and unsubstitutedbisbenzylidene sorbitols, benzoxazinone UV absorbers such as2,2′-p-phenylene-bis(3,1-benzoxazin-4-one), Cyasorb® 3638 (CAS#18600-59-4), and blowing agents.

In general, the compounds of component (b) of the present invention areemployed in from about 0.01 to about 5% by weight of the stabilizedcomposition, although this will vary with the particular substrate andapplication. An advantageous range is from about 0.05 to about 3%, andespecially 0.05 to about 1%.

The UVA's of component (b) as well as further optional additives, may beincorporated into the polymeric substrate according to methods known tothose skilled in the art.

The UVA's of component (b) and optional further additives may be addedto the polymer to be stabilized either separately or together.

The present stabilizers of component (b) of this invention and optionalfurther additives may be applied to or incorporated in the polymericsubstrate for example by melt blending, solution blending, solutioncasting or adsorption from solution.

For example, additives of component (b) and optional further additivesmay be incorporated in the polymeric substrate before or after moldingor also by applying the dissolved or dispersed additive mixture to thepolymeric substrate, with or without subsequent evaporation of thesolvent. Additives of component (b) and optional further additives canalso be added to the polymeric substrate in the form of a masterbatchwhich contains these components in a concentration of, for example,about 2.5% to about 50% by weight.

For example, the additives of component (b), optional further additivesand the polymeric substrate may all be dissolved in a mutuallycompatible solvent wherein the concentration of polymer in the solventranges from about 5 to about 50% by weight of the solvent. The solutionmay then be dried at an appropriate temperature to produce a cast filmcontaining a blend of polymer and the additive(s).

Alternatively, additive compounds of component (b) and optional furtheradditives are blended into a polymeric substrate by dissolving theadditive(s) in a volatile solvent to provide a solution with an additiveconcentration of about 5 to about 50% by weight. The solution is thenmixed with the polymer and the mixture is dried thereby providingpolymer particles which are substantially evenly coated withadditive(s). The coated polymer particles may then be fed to an extruderwherein the mixture is melt blended and extruded to produce an extrudatecontaining the polymeric substrate and additive(s).

If in a liquid form, the stabilizers of component (b) may be applieddirectly to polymer particles by stirring the polymer particles in theliquid additive mixture until the additive mixture is evenly dispersedon the surface of the polymer particles. The polymer may then be fed toan extruder to produce an extrudate of polymer substrate containing theadditives.

The compositions of this invention may also be prepared by submittingthe stabilizers of component (b), optional further additives and solidpolymeric material to an extruder followed by melt blending andextruding the molten mixture. Alternatively, the polymeric material andadditives may be melt blended in a thermostatted vessel where thecomponents are in molten form, followed by cooling of the mixture.

Component (b) and optional further additives can also be added before orduring the polymerization or before crosslinking.

Component (b) and optional further additives can be incorporated intothe polymeric substrate in pure form or encapsulated in waxes, oils orpolymers.

Component (b) and optional further additives can also be sprayed orcoated onto the polymeric substrate. It may be used to dilute otheradditives (for example the conventional additives indicated above) ortheir melts so that it can be sprayed or coated together with theseadditives onto the polymeric substrate. Addition by spraying during thedeactivation of the polymerization catalysts is particularlyadvantageous, it being possible to carry out spraying using, forexample, the steam used for deactivation.

In the case of spherically polymerized polyolefins it may, for example,be advantageous to apply component (b) optionally together with otheradditives, by spraying.

For instance, component (b) and optional further additives areincorporated into the polymeric substrate of component (a) by meltblending.

The compositions of the present invention can be used in various forms,for example as films, fibers, ribbons, molded materials, profiles or asbinders for paints, adhesives or cement.

The following Examples are meant for illustrative purposes only.

SYNTHETIC EXPERIMENTAL PROCEDURES

A) Benzoxazinones

The general synthetic scheme for the preparation of the presentbenzoxazinone UVA's is as below:

Example A1 2-Amino-5-α-cumylbenzoic Acid

A mixture of anthranilic acid (82 g, 0.6 mol), α-methylstyrene (168 mL,1,28 mol), zinc chloride (82 g, 0.6 mol) and concentrated hydrochloricacid (100 mL) is heated to 120° C. for four hours. The mixture is cooledand diluted with water (100 mL). The pH is adjusted to approximately 4using 50% sodium hydroxide. The resulting solids are collected, washedwith water and then partitioned between methylene chloride and water.The pH is adjusted to 5-6 with dilute hydrochloric acid giving two clearphases. The organic phase is separated and then dried over anhydroussodium sulfate. The methylene chloride is removed and the solid residueobtained is recrystallized from heptane/toluene giving the titleintermediate compound as a white solid melting at 142-144° C.

Example A2 2-Amino-5-methoxybenzoic Acid

This compound is prepared according to the procedure described inOrganic Preparation and Procedures Int., 13, 189 (1981).

Example A3 4-Amino-biphenyl-3-carboxylic Acid

Methyl 4-amino-biphenyl-3-carboxylate is prepared according to theprocedure described in WO 99/462,237.

Methyl 4-amino-biphenyl-3-carboxylate (15.2 g, 0.67 mol) is dissolved inethanol (100 mL) and a solution of sodium hydroxide (3.0 g, 0.75 mol) in20 mL of water is added. The resulting solution is heated to 50° C. forfive hours. The mixture is then cooled and the pH adjusted to about 4with hydrochloric acid. Some insoluble material is removed byfiltration. The filtrate is then diluted with 100 mL of water and thesolid formed is collected. The solid is purified by dissolving in dilutesodium hydroxide solution, extraction with ethyl acetate andreacidification to pH 4 with hydrochloric acid. The title intermediatecompound is obtained as a light brown solid melting at 208-209° C.

Example A4 4-Phenylsulfonylbenzoyl Chloride

Preparation 1 of WO 96/262,196 described the reaction of sodiumbenzenesulfinate (43 g, 0.26 mol) and 4-fluoroaceto phenone (30 g, 0.22mol) at 130° C. in dimethyl sulfoxide (200 mL) for 48 hours. The mixtureis then poured into 1000 mL of water. The solid formed is colled anddried to give 50 g of 1-(4-phenylsulfonyl-phenyl)-ethanone. This solidis suspended in ethanol (350 mL), heated to 60° C. and treated asdescribed in J. Med. Chem., 34, 3295 (1991) to give 4-phenylsulfonylbenzoic acid melting at 269-271° C. A suspension of 4-phenylsulfonylbenzoic acid (15 g, 0.57 mol) in toluene (50 mL) is treated withthionyl chloride (25 mL). A few drops of N,N-dimethylformamide are addedand the suspension is heated to 70° C. for three hours. The solution isconcentrated to give the title intermediate compound which is usedwithout further purification.

The following benzoxazin-4-ones are made according to the generalprocedure described in Example 24 below. The acid chlorides used arecommercially available or made by reacting the respective carboxylicacid with thionyl chloride as described in Example 23.

Example A5 2-(4-Trifluoromethylphenyl)-6-α-cumyl-4H-3,1-benzoxazin-4-one

To a solution of 2-amino-5-α-cumylbenzoic acid (13.5 g, 0.53 mol,prepared in Example 20) and triethylamine (7.8 g, 0.56 mol) intetrahydrofuran (200 mL) is added dropwise at room temperature asolution of 4-trifluoromethylbenzoyl chloride (11 g, 0.53 mol). Theresulting suspension is stirred at room temperature overnight, thenfiltered and concentrated to a solid that is then suspended in aceticanhydride and heated to 115° C. for three hours. The resulting solutionis cooled and concentrated to an oil. The oil is taken up in ethanol(100 mL) and allowed to stand. The resulting solid formed is colled anddried to give 15.4 g of the title compound melting at 104-105° C. Thestructure of the compound is confirmed by ¹Hnmr (CDCl₃) 500 MHz: δ 1.78(s, 6H); 7.23 (t, 1H); 7.23 (d, 2H); 7.31 (t, 2H); 7.60 (d, 1H); 7.64(dd, 1H); 7.78 (d, 2H); 8.26 (d, 1H). ¹⁹Fnmr (fluorinated species at−69.57 ppm).

Example A6

-   2-phenyl-6-α-cumyl-4H-3,1-benzoxazin-4-one; melts at 109-111° C.;

Example A7

-   2-(3-trifluoromethylphenyl)-6-methoxy-4H-3,1-benzoxazin-4-one; melts    at 110-111° C.;

Example A8

-   2-(2-trifluoromethylphenyl)-6-methoxy-4H-3,1-benzoxazin-4-one; melts    at 98-100° C.;

Example A9

-   2-(4-trifluoromethylphenyl)-6-methoxy-4H-3,1-benzoxazin-4-one; melts    at 137-138° C.;

Example A10

-   2-(4-bromophenyl)-6-methoxy-4H-3,1-benzoxazin-4-one;

Example A11

-   2-(4-phenylphenyl)-6-methoxy-4H-3,1-benzoxazin-4-one;

Example A12

-   2-(4-phenylsulfonylphenyl)-6-methoxy-4H-3,1-benzoxazin-4-one;

Example A13

-   2-(3-trifluoromethylphenyl)-6-α-cumyl-4H-3,1-benzoxazin-4-one; melts    at 97-99° C.;

Example A14

-   2-(4-methoxyphenyl)-6-α-cumyl-4H-3,1-benzoxazin-4-one; melts at    135-137° C.;

Example A15

-   2-(2-methoxyphenyl)-6-α-cumyl-4H-3,1-benzoxazin-4-one; melts at    119-121° C.;

Example A16

-   2-(3-methoxyphenyl)-6-α-cumyl-4H-3,1-benzoxazin-4-one; melts at    136-137° C.;

Example A17

-   2-(3-methylphenyl)-6-α-cumyl-4H-3,1-benzoxazin-4-one; melts at    164-165° C.;

Example A18

-   2-(4-methoxycarbonylphenyl)-6-α-cumyl-4H-3,1-benzoxazin-4-one; melts    at 150-152° C.;

Example A19

-   2-(3-methoxycarbonylphenyl)-6-α-cumyl-4H-3,1-benzoxazin-4-one; melts    at 165-167° C.;

Example A20

-   2-(4-phenylsulfonylphenyl)-6-α-cumyl-4H-3,1-benzoxazin-4-one; melts    at 148-150° C.; and

Example A21

-   2-(3-trifluoromethylphenyl)-6-phenyl-4H-3,1-benzoxazin-4-one; melts    at 154-155° C.

According to the above procedures, the following benzoxazinones areprepared:

Example A22

mp 155-156° C.,

Example A23

mp 258-260° C., and

Example A242-(2-trifluoromethylphenyl)-6-α-cumyl-4H-3,1-benzoxazin-4-one,consistent with proton NMR Example A254-(4-methyphenyl)-6-α-cumyl-4H-3,1-benzoxazin-4-one, consistent withproton NMR

Oxanilides are prepared for example according to the following generalscheme:

B) Oxanilides

Example B1 N-(4-Dodecyloxyphenyl)oxalamic acid ethyl ester

In a 1 L jacketed flask under a nitrogen atmosphere is added 60 g(0.2425 mols) of p-dodecyloxyaniline, 650 mL of CH₂Cl₂ and 56.6 g ofpyridine (0.716 mols) and the resulting solution is cooled to 0° C.Maintaining an internal temperature below 5° C., 46.3 g (0.339 mols) ofethyl chlorooxoacetate is then added dropwise over a period of one hour.After the addition is complete, the internal temperature is maintainedat 10° C. overnight. To the resultant reaction mixture is added rapidly400 mL of 1N HCl and the resultant mixture is allowed to warm to RT. Thereaction mixture is stirred for one hour than the organic phaseseparated. The organic phase is dried over anhydrous sodium sulphate andisolubles removed by filtration. The volatiles are removed in vacuo andthe residue is recrystallized from ethanol (250 mL). The solid is washedtwice with ethanol (50 mL) at 0° C. to give 64.1 g of a white solid, mp.70.5-72° C. The NMR, MS and IR spectra are consistent with the product.

Example B2 N-(4-Dodecyloxyphenyl)-N′-(4-phenyloxyphenyl)oxalamide

A solution of N-(4-dodecyloxyphenyl)oxalamic acid ethyl ester (10 g,0.026 mol), 4-phenoxyaniline (5 g, 0.026 mol) and lithium t-butoxide(0.2 g, 0.0026 mol) in xylene (50 mL) is heated to gentle reflux. Adistillate of ethanol/xylene is slowly collected; the reaction volumn iskept at 50 mL by adding xylene. Heating and distillation continued for 3hours. The reaction mixture is cooled, the solids are collected andwashed sequentially with warm ethyl acetate, ethanol, water and finallyethanol. There is obtained 11.5 g white solid mp: 179-181.

Following the procedures of example 1 and example 2, the followingdodecyloxy oxalamides are prepared.

Example B3 N-(4-Dodecyloxyphenyl)-N′-(4-methoxyphenyl)oxanilide

Product obtained as a slight greyish solid sinters at 200-205° C. andhas a final mp>250° C. Product verified by NMR, MS and IR.

Example B4 N-(4-Dodecyloxyphenyl)-N′-(p-toluyl)-oxanilide

Product obtained as a white powder approximately 96% pure by NMR and MSwith mp 184-192° C. Product verified by NMR, MS and IR.

Example B5 N-(4-cyanophenyl)-N′-(4-Dodecyloxyphenyl)oxanilide

Product obtained as a slight beige powder which sinters at 194-198° C.and has a mp>250° C. Product verified by NMR, MS, and IR. Expected % C:72.13, % H, 7.85, % N: 9.35; Found: % C: 72.11, % H, 8.17, % N, 8.94.

Example B6 N-(4-Dodecyloxyphenyl)-N′-(3-methoxyphenyl)oxanilide

Product obtained as a white powder which sinters at 160-163° C. and hasa final mp>250° C. Product verified by NMR, MS, and IR. Expected % C:71.34, % H, 8.43, % N: 6.16; Found: % C: 70.93, % H, 8.26, % N, 5.78.

Example B7 N-(4-Dodecyloxyphenyl)-N′-(3-toluyl)oxanidide

Product obtained as a white powder with mp 139-141° C. Product verifiedby NMR, MS and IR.

Example B8 N-(3-cyanophenyl)-N′-(4-Dodecyloxyphenyl)oxanilide

Product obtained as a white powder with mp 165-168° C. Product Verifiedby NMR, MS, and IR.

Example B9 N-(4-Dodecyloxyphenyl)-N′-(3-trifluoromethylphenyl)-oxanilide

Product obtained as a white solid with mp 143-145° C.: Product verifiedby NMR, MS and IR. Expected % C: 65.84, % H, 7.16, % N: 5.69; Found: %C: 65.80, % H, 6.82, % N, 5.72

Example B10N-(4-Dodecyloxyphenyl)-N′(4′-trifluoromethyl-1,1′-biphen-4-yl)-oxanilide

The title oxanilide is prepared fromN-(4-bromophenyl)-N′-(4-Dodecyloxyphenyl)oxanilide,4-trifluoromethylphenylboronic acid, palladium(II) diacetate,triphenylphosphine, 3 mL of 2M sodium carbonate, 5 mL of water, and 200mL of 1-propanol. MS m/z 568.

Example B11N-[4-(2-Ethylhexyloxy)phenyl]-N′-(3′-trifluoromethyl-1,1′-biphen-4-yl)-oxanilide

4-Amino-3′-trifluoromethyl-1,1′-biphenyl: To a mixture of 3.44 g (0.02mol) of 4-bromoaniline and 4.50 g (0.024 mol) of3-trifluoromethylphenylboronic acid in 200 mL of 1-propanol that isevacuated and filled with nitrogen (3×) is added sequentially 0.18 grams(0.8 mmol) of palladium(II) acetate, 0.630 (2.4 mmol) oftriphenylphosphine, 12 mL of 2M aqueous sodium carbonate, and 10 mL ofdistilled water. The reaction mixture is evacuated and filled withnitrogen (3×) and then stirred for 10 minutes. The reaction mixture isheated at 76° C. for 5.5 hours. The solvent is removed in vacuo and theresidue purified sequentially by dry-column chromatography (7:3toluene:ethyl acetate eluent) and dry-column flash chromatography(toluene eluent) to give 2.38 grams of a light amber liquid. Flowinjection LC/AP_(C)/MS m/z 238 (M+H).

A mixture of 2.17 g (9.1 mmol) of4-amino-3′-trifluoromethyl-1,1′-biphenyl, 3.21 g (10 mmol) ofN-[4-(2-ethylhexyloxy)phenyl]oxalamic acid ethyl ester, 0.8 g (1 mmol)of lithium tert-butoxide in 45 mL of m-xylene is heated at reflux for 8hours. The reaction mixture is cooled an the solid collected byfiltration. The solid is purified by recrystallization from toluene andthen triturated with acetonitrile to give 1.39 grams (30%) of a whitesolid mp 143-146° C. MS: m/z 512; UV (ethyl acetate) lambda max 298(molar extinction 26,408). Anal. Calcd for C₂₉H₃₁F₃N₂O₃: C, 67.96; H,6.10; N, 5.47. Found: C, 67.49; H, 6.30; N, 5.43.

N-[4-(2-Ethylhexyloxy)phenyloxalamic acid ethyl ester:4-(2-ethylhexyoxy)aniline is prepared according to the proceduredescribed in U.S. Pat. No. 5,484,696. The oxalamic acid ethyl ester isprepared according to the procedure described in Example 1. Productconfirmed by NMR.

Example B12N-[2-(2-Ethylhexyloxy)phenyl]-N′-(3′-trifluoromethyl-1,1′-biphen-4-yl)-oxanilide

The procedure of example 11 is repeated usingN-[2-(2-ethylhexyloxy)phenyl]oxalamic acid ethyl ester in place ofN-[4-(2-ethylhexyloxy)phenyl]oxalamic acid ethyl ester.

Example B13 4-Dodecyloxy-4′-trifluoromethyloxanilide

This compound is made according to the general procedures as describedabove. The product sinters in a melting tube as 225-231° C. andmelts >250° C. Structure confirmed by ¹H NMR, MS and IR.

C) Benzylidene Malonates

Benzylidene malonates are prepared according to the following generalprocedure:

The general synthetic scheme involves reaction of an appropriatelysubstituted benzoic acid with dimethyl malonate in the present ofpyridine and toluene.

The compounds prepared are substituted on the benzylidene ring in theortho, meta and para positions by an electron withdrawing (EW)trifluoromethyl groups and by electron donating (ED) groups methyl,phenyloxy and methoxy.

Photographic studies indicate that substitution that photopermanence canbe substantially improved by substitution of the two ortho positions bymethoxy moieties.

Early work in poly(methyl methacrylate) indicate that these compoundsare very stable.

Some eight benzylidenemalonate compounds are prepared using the generalprocedure given below. The structures of each of the compounds isconfirmed by ¹ Hnmr analysis.

Example C1 Dimethyl 2.4-Dimethoxybenzylidenemalonate

2,4-Dimethoxybenzaldehyde (10.0 g, 0.060 mol), dimethyl malonate (9.5 g,0.072 mol), piperidine (1.5 g, 0.017 mol), benzoic acid (1.8 g, 0.015mol) and 100 mL of toluene are stirred at reflux for 5.5 hours under aDean Stark trap to remove water. After cooling to room temperature, thereaction mixture is partitioned between ethyl acetate and water. Theorganic layer is washed with 10% hydrochloric acid, water and brine. Theresulting solution is dried over anhydrous magnesium sulfate and thenconcentrated to yield 17.8 g of an orange syrup which is purified bychromatography on silica gel (2:1, heptane:ethyl acetate) to provide12.8 g of the title compound as a pale yellow solid melting at 71-73° C.

Example C2 Dimethyl 2,4,6-Trimethoxybenzylidenemalonate

Following the procedure given above, 9.8 g of the title compound isprepared from 2,4,6-trimethoxybenzaldehyde as a white solid melting at123-125° C. after recrystallization from heptane/ethyl acetate.

Example C3 Dimethyl 2,4,6-Trimethylbenzylidenemalonate

Following the procedure given above, 9.6 g of the title compound isprepared from 2,4,6-trimethylbenzaldehyde as a pale yellow oil afterpurification by chromatography on silica gel (15:1, heptane:ethylacetate).

Example C4 Dimethyl 4-Trifluoromethylbenzylidenemalonate

Following the procedure given above, 5.5 g of the title compound isprepared from 4-trifluoromethylbenzaldehyde as a white solid melting at49-50° C. after recrystallization from heptane/ethyl acetate.

Example C5 Dimethyl 3-Trifluoromethylbenzylidenemalonate

Following the procedure given above, 6.2 g of the title compound isprepared from 3-trifluoromethylbenzaldehyde as a white solid melting at53-54° C. after recrystallization from heptane/ethyl acetate.

Example C6 Dimethyl 4-Phenoxybenzylidenemalonate

Following the procedure given above, 9.8 g of the title compound isprepared from 4-phenoxybenzaldehyde as a yellow syrup.

Example C7 Dimethyl 2-Methoxy-1-naphthylidenemalonate

Following the procedure given above, 9.3 g of the title compound isprepared from 2-methoxy-1-naphthaldehydeas a yellow solid melting at78-81° C. after purificiation by chromatography on silica gel (3:1,heptane:ethyl acetate).

Example C8 Dimethyl 2.2-Diphenylethylidenemalonate

This compound is made by the procedure of N. J. Head, G. A. Olah and G.K. Surya Prakash, J. Am. Chem. Soc., 117, 11205 (1995).

To a stirred solution of titanium tetrachloride (22 mL, 0.2 mol), carbontetrachloride (50 mL) and tetrahydrofuran (400 mL) at 0° C. is addedbenzophenone (18.2 g, 0.1 mol) and dimethyl malonate (13.3 g, 0.1 mol).After stirring at 0° C. for forty minutes, a solution of pyridine (32mL) in tetrahydrofuran (70 mL) is added dropwise. The mixture is allowedto warm to room temperature and is then stirred for four days. Theformation of a heavy precipitate requires the addition of moretetrahydrofuran to facilitate stirring. Water (100 mL) and ethyl acetate(100 mL) are then added. The mixtures separates into two layers. Theaqueous layer is extracted with additional ethyl acetate. The combinedorganic layers are washed with brine, sodium bicarbonate and more brine.The solution is then dried over anhydrous magnesium sulfate andconcentrated. The crude material is a white semi-solid slurry which isthen recrystallized twice from heptane/ethyl acetate to afford 11.3 g ofthe title compound as a white solid melting at 120-122° C.

D) Quinazolines

The general synthetic scheme involves reacting2,4-dihydroxyisoquinaoxaline with phosphorus oxychloride, a tert-amineat 130° C., then with aluminum chloride, and resorcinol in sulfolane at60° C. to give an intermediate substituted by a chloro group on the ringcontaining the two N-atoms. The intermediate with the chloro group orwith the free hydroxyl group on the phenyl ring can they be used toprepare novel UV absorbers containing either ED or EW moieties.

Quinazolines are prepared for example according to the following generalprocedures:

E) Benzotriazoles

General synthetic procedures for benzotriazole ring construction arelocated in U.S. Pat. Nos. 5,977,219 and 6,166,218, the disclosures ofwhich are hereby incorporated by reference. To ensure compounds of highpurity are tested, all final products are chromatographed on silica geland sublimed except the compound of Example 3 which is chromatographedtwice on silica gel.

Example E1

Isolated as a white solid; melting point=111-112° C.; ¹HNMR (500 MHz,CDCl₃): δ=8.29 (m, 2H), 7.93 (m, 2H), 7.42 (m, 2H), 7.07 (m, 2H), 3.91(s, 3H); MS m/z: 225, 210, 182. Anal. Calcd. for C₁₃H₁₁N₃O: C, 69.32; H,4.92; N, 18.65. Found: C, 69.10; H, 4.80; N, 18.65.

Example E2

The synthesis of this compound followed the same synthetic conditionsused for Example 3. Isolated as a white solid; melting point=128-128.5°C.; ¹HNMR (300 MHz, CDCl₃): δ=8.00 (m, 2H), 7.85 (s, 1H), 7.42 (m, 2H),7.30 (s, 1H), 5.22 (m, 1H), 3.43 (dd, 1H), 2.93 (dd, 1H), 1.76 (s, 2H),1.56 (s, 3H), 1.42 (s, 6H), 0.80 (s, 9H). MS m/z: 364 (M+H). Anal.Calcd. for C₂₃H₂₉N₃O: C, 76.00; H, 8.04; N, 11.56. Found: C, 75.94; H,7.98; N, 11.42.

Example E3

5-Trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole (13.01 g, 0.033 mol), potassium hydroxide (2.37 g, 0.036 mol) and ethanol(60 mL) are charged to a lab reactor and stirred at ambient temperaturefor two hours. Allyl bromide (4.84 g, 0.039 mol) and potassium iodide(0.34 g, 0.002 mol) are added to the reaction mixture which is heated to85° C. After holding at 85° C. for 4.5 hours, the solvent is removed andreplaced with 100 mL of heptane. The mixture is washed thrice with 40 mLof water. The solvent is then removed to yield 14.2 g of thecorresponding O-allyl ether as an off-white solid. ¹HNMR (300 MHz,CDCl₃): δ=8.35 (s, 1H), 8.20-8.12 (d, 1H), 7.67-7.61 (m, 2H), 7.54-7.49(dd, 1H), 7.11-7.06 (d, 1H), 6.00-5.86 (m, 1H), 5.34-5.16 (m, 2H),4.65-4.60 (d, 2H), 1.77 (s, 1H), 1.41 (s, 6H), 0.78 (s, 9H).

The O-allyl compound (14.2 g) as prepared above is charged to a reactorand heated to 190-195° C. and held at that temperature for five hours.Flash column chromatography with silica gel and ethyl acetate/heptanesolvent as the eluent yielded the allyl-substituted benzotriazolecompound (12.2 g) as a yellow oil. MS m/z: 432 (M+H); ¹HNMR (300 MHz,CDCl₃): δ=11.17 (s, 1H), 8.35-8.29 (m, 2H), 8.12-8.05 (d, 1H), 7.72-7.66(dd, 1H), 7.34-7.29 (d, 1H), 6.18-6.02 (m, 1H), 5.20-5.06 (m, 2H),3.64-3.53 (d, 2H), 1.81 (s, 2H), 1.46 (s, 6H), 0.78 (s, 9H).

5-Trifluoromethyl-2-(2-hydroxy-3-allyl-5-tert-octyl-phenyl)-2H-benzotriazole(12.16 g, 0.028 mole), methanesulfonic acid (3.34 g, 0.034 mole) andchlorobenzene (50 mL) are charged to a reaction flask fitted with thenecessary auxiliary equipment. The reaction mixture is heated to 14° C.and held there for three hours. After removal of solvent, the brown oilis chromatographed on silica gel using 19:1 hexane/ethyl acetate as theeluent. After second silica gel chromatography, the desired product isobtained as a yellow viscous resin. ¹HNMR (300 MHz, CDCl₃): δ=8.36 (s,1H), 8.12 (d, 1H), 7.87 (s, 1H), 7.60 (d, 1H), 7.35 (s, 1H), 5.21 (m,1H), 3.47 (dd, 1H), 2.94 (dd, 1H), 1.79 (s, 2H), 1.57 (d, 3H), 1.44 (s,6H), 0.8 (s, 9H); MS m/z: 432 (M+H). Anal. Calcd. for C₂₄H₂₈F₃N₃O: C,66.81; H, 6.54; N, 9.74. Found: C, 66.10; H, 6.25; N, 9.76.

Example E4

Isolated as a light yellow solid; melting point=127.5-128.5° C.; ¹HNMR(300 MHz, CDCl₃): δ=8.38 (s, 1H), 8.15 (d, 1H), 7.71 (s, 1H), 7.68 (dd,1H), 7.25 (d, 1H), 6.96 (d, 1H), 2.35 (s, 3H), 2.27 (s, 3H). MS m/z: 308(M+H). Anal. Calcd. for C₁₅H₁₂F₃N₃O: C, 58.63; H, 3.94; N, 13.67. Found:C, 58.66; H, 3.71; N, 13.60.

Example D5

Isolated as a white solid; melting point=135-136° C.; ¹HNMR (500 MHz,CDCl₃): δ=8.33 (d, 1H), 8.09 (d, 1H), 7.65 (dd, 1H), 7.31 (d, 1H), 6.78(d, 1H), 5.30 (broad s, 1H), 2.29 (s, 3H), 2.14 (s, 3H). ¹⁹FNMR (300MHz, CDCl₃, CF₃COOH @−70 ppm)): −68.9 ppm. Anal. Calcd. for C₁₅H₁₂F₃N₃O:C, 58.63; H, 3.94; N, 13.67. Found: C, 58.53; H, 3.88; N, 13.72.

Example E6

Isolated as a white solid; melting point=109-111° C.; ¹HNMR (300 MHz,CDCl₃): δ=8.34 (s, 1H), 8.10 (d, 1H), 7.63 (dd, 1H), 7.42 (d, 1H), 6.88(d, 1H), 3.92 (s, 3H), 2.27 (s, 3H), 2.15 (s, 3H). MS m/z: 322 (M+H).Anal. Calcd. for C₁₆H₁₄F₃N₃O: C, 59.81; H, 4.39; N, 13.08. Found: C,59.65; H, 4.10; N, 13.08.

Example E7

Isolated as a white solid; melting point=121.5-122.5° C.; ¹HNMR (300MHz, CDCl₃): δ=8.00 (m, 2H), 7.44 (m, 2H), 7.30 (d, 1H), 6.84 (d, 1H),3.72 (s, 3H), 2.30 (s, 3H), 1.81 (s, 3H). MS m/z: 254 (M+H). Anal.Calcd. for C₁₅H₁₅N₃O: C, 71.13; H, 5.97; N, 16.59. Found: C, 71.01; H,5.82; N, 16.75.

Example E8

Isolated as a white solid; melting point=166.5-167.5° C.; ¹HNMR (300MHz, CDCl₃): δ=8.04 (s, 1H), 8.00 (m, 2H), 7.51 (m, 2H), 7.21 (d, 1H),6.95 (d, 1H), 2.34 (s, 3H), 2.32 (s, 3H); MS m/z: 240 (M+H). Anal.Calcd. for C₁₄H₁₃N₃O: C, 70.28; H, 5.48; N, 17.56. Found: C, 70.02; H,5.58; N, 17.53.

Example E9

Isolated as a light yellow solid; melting point=189-190° C.; ¹HNMR (300MHz, CDCl₃): δ=7.94 (m, 2H), 7.46 (m, 2H), 7.30 (d, 1H), 6.78 (d, 1H),5.19 (s, 1H), 2.28 (s, 3H), 2.14 (s, 3H). MS m/z: 240 (M+H). Anal.Calcd. for C₁₄H₁₃N₃O: C, 70.28; H, 5.48; N, 17.56. Found: C, 70.06; H,5.51; N, 17.65.

Example E10

Isolated as a white solid; melting point=110-110.5° C.; ¹HNMR (300 MHz,CDCl₃): δ=7.94 (m, 2H), 7.44 (m, 2H), 7.41 (d, 1H), 6.85 (d, 1H), 3.91(s, 3H), 2.28 (s, 3H), 2.14 (s, 3H); MS m/z: 254 (M+H). Anal. Calcd. forC₁₅H₁₅N₃O: C, 71.13; H, 5.97; N, 16.59. Found: C, 71.03; H, 5.81; N,16.69.

Example E11

Isolated as a white solid; melting point=143-143.5° C.; ¹HNMR (300 MHz,CDCl₃): δ=11.04 (s, 1H), 8.14 (s, 1H), 7.95 (m, 2H), 7.46 (m, 2H), 7.01(s, 1H), 2.32 (s, 3H), 2.31 (s, 3H). MS m/z: 240 (M+H). Anal. Calcd. forC₁₄H₁₃N₃O: C, 70.28; H, 5.48; N, 17.56. Found: C, 69.98; H, 5.40; N,17.63.

Example E12

Isolated as a light yellow solid; ¹HNMR (300 MHz, CDCl₃): δ=8.36 (s,1H), 8.11 (d, 1H), 7.65 (dd, 1H), 7.35 (d, 1H), 6.86 (d, 1H), 3.72 (s,3H), 2.31 (s, 3H), 1.81 (s, 3H). MS m/z: 322 (M+H). Anal. Calcd. forC₁₆H₁₄F₃N₃O: C, 59.81; H, 4.39; N, 13.08. Found: C, 59.58; H, 4.03; N,13.11.

Example E13

According to the general procedures as herein described, the followingbenzotriazoles are prepared:

F) Application Examples

Application Example F1 Benzoxazinones

The following compounds are employed in the working Examples:

compound R₂ R₃ R₄ preparation example 118 H H CF₃ A5  119 H H OCH₃ A14176 OCH₃ H H A15 109 H OCH₃ H A16 108 H CH₃ H A17 116 H CF₃ H A13 174CF₃ H H A24 120 H H CH₃ A25 110 H H COOMe A18 dicumyl H H

A23

The photostabilty of representative benzoxazinones is determined byincorporation into solution and polymer films and monitoring the lossafter exposure to UV radiation. Loss is measured by UV absorption.

Solution

The selected benzoxazinones are dissolved in ethyl acetate at the givendilutions and the initial UV spectrum obtained. A portion of thesolutions are transferred into borosilicate vials with teflon coatedcaps and photolyzed in a Rayonet Photochemical Reactor (The Southern NewEngland Ultraviolet Company) fitted with 4 300 nm lamps and 12 350 nmlamps. To ensure equal exposure for all samples the vials are mounted ona merry-go-round unit which revolved at 5 RPM. At selected intervals thesamples are removed and the loss of compound is obtained by measuringthe loss of UV absorption at the benzoxazinone lambda max. Such lossrates are typically independent of concentration for samples with UVabsorbances of greater than 0.8 (lyengar, R., Schellenberg, B., Polym.Degrad. Stab., 61, 151 (1998), Pickett, J. E., Macromol. Symp., 115,127(1997), Pickett, J. E., Moore, J. E, Die Angew. Makromol. Chem., 232,229 (1995).) Results are in the table below. Absorbance Abs compoundg/100 mL max 0 h 18 h 42 h ΔA ΔA/100 h 118 2.2 305 nm 1.81 1.79 1.770.04 0.10 119 3.3 308 nm 1.65 1.56 1.44 0.21 0.50 dicumyl 2.1 354 nm1.57 1.51 1.43 0.14 0.33 ME 2.2 300 nm 1.73 1.53 1.06 0.67 1.59ΔA is the loss of absorption at lambda max for the overall exposuretime.ΔA/100 h is the loss rate expressed in terms abs units per 100 hours.

Similar results are obtained in cyclohexane

The compound substituted with the CF₃ electron withdrawing group isshown to be extremely photostable in polar and non-polar solvents.

The enhanced photostability of the compounds of this invention areconfirmed in polymeric compositions.

Polycarbonate Films

PC (polycarbonate) films, 1 mil thick, are cast from room temperaturemethylene chloride solutions of polycarbonate flake (Lexan® 145, GEPlastics) and between 1 and 3% benzoxazinone derivative (wt % based onpolycarbonate) using a calibrated drawdown bar. The free standing filmsare mounted in cardboard holders, secured in metal frames and exposed inan Atlas Ci65 xenon arc weatherometer under dry conditions (ASTM G26).Loss of UVA is determined by monitoring loss of absorbance at 345 nm.This wavelength is selected to minimize the impact of polycabonatedegradation products which absorb in the UV. Results are below.Absorbance compound 0 h 250 h 500 h 750 h ΔA ΔA/100 h 119 (2.08%) 3.022.21 2.00 1.65 1.37 1.8/h 118 (2.29%) 1.95 1.95 1.95 1.95 unchanged

After 750 hours the PC decomposition products began to skew the UVabsorption results.

Polymethyl(methacrylate) Films

Polymethyl (methacrylate) films, 1 mil thick, are cast from roomtemperature methylene chloride solutions of polymethyl (methacrylate),medium molecular weight, Aldrich and between 1 and 3% benzoxazinonederivative (wt % based on polymer) using a calibrated drawdown bar. Thefree standing films are mounted in cardboard holders, secured in metalframes and exposed in an Atlas Ci65 xenon arc weatherometer under dryconditions (ASTM G26). Loss of UVA is determined by monitoring loss ofabsorbance at the maximum nearest 300 nm (ΔA). Due to excessive noise inthe UV spectra at 0 hours, data on rate loss is tabulated for mostsamples beginning at 250 hours of exposure, after a smooth loss rate isobserved to eliminate scatter. Results are below. Absorbance compound 0h 250 h 500 h 750 h 1000 h 1500 h 2000 h 176 (2.08%, 2.7 0.5 — — — — —300 nm) 109 (2.08%, — 2.47 2.18 1.78 1.43 — — 304 nm) 108 (1.99%, — 3.032.80 2.38 2.11 — — 304 nm) 116 (2.29%, — 3.33 3.25 2.92 2.67 2.43 2.17305 nm) 174 (2.29%, — 3.07 3.02 2.77 2.64 2.43 2.22 280 nm)Average loss per 100 h, 250-1000 hours exposure (ΔA @ 1000 h/7.5):Compound

109: 1.04/7.5=0.14

108: 0.92/7.5=0.12

116: 0.66/7.5=0.09

174: 0.43/7.5=0.06

The compounds of the instant invention are more stable in PC and PMMAthan similar compounds bearing alternate substitution patterns.

Photographic Compositions

A gelatin coat of the following composition (per m²) is applied in thecustomary manner to a polyester base. Components Amount Gelatin 1200 mg Tricresyl Phosphate 510 mg Hardener*  40 mg Wetting Agent** 100 mg TestUV Absorber 400 mg*potassium salt of 2-hydroxy-4,6-dichloro-s-triazine**sodium 4,8-diisobutylnaphthalene-2-sulfonate

The gelatin coats are dried at 20° C. for seven days.

When the instant UV absorbers are used, clear transparent coats areobtained which are suitable for photographic recording material forexample as a UV filter coat.

The benzoxazinones of this invention are more permanent than others uponexposure to 60 KJ of UV photography as measured by loss of opticaldensity: % change in OD compound 30 KJ 60 KJ 120 13 60 110 17 40 118 812 116 5 6Polycarbonate Films

Polycarbonate films of about 1 mil thickness and containing a UVabsorber are prepared for dissolving polycarbonate granules (LEXAN® 145,General Electric) and UV absorbers in methylene chloride and casting thefilms on a glass plate using a drawdown bar. The films are exposed for250 hours in a Xenon arc Weather-Ometer according to ASTM G26 testmethod and the color change (delta YI) versus that for unexposed filmsare recorded below. The color measurements (yellowness index —YI) arecarried out on an ACS spectrophotometer, small area view, spectralcomponent included d/8, D65, 10° observer, YI 1925 for unexposed andexposed samples. Delta YI Additive (weight percent) 1000 hours 2000hours Blank (no stabilizer) 14.9 20.5 Tinuvin ® 234 (2.50%) 2.6 7.6Compound 118 (2.29%) 4.5 9.2 Compound 119 (2.08%) 15.8 20.1Tinuvin ® 234 is 2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole.

These data show that the instant compounds are efficacious when used inthermoplastic compositions, as evidenced in low delta YI measurements.

Application Example F2 Malonates

The following table illustrates a desireable red shift of di and trimethoxy substituted benzylidene malonates substituted at the 2-positionvs. those substituted at the 3-position: methoxy postition λmax 2, 4 3322, 3 283 3, 4 327 2, 4, 6 326 3, 4, 5 313

A red shift is generally desireable for UV absorbers and results in abroader spectral coverage.

Other positions are unsubstituted (hydrogen).

Solution

Ethyl Acetate solutions of various benzylidene malonate derivatives, ˜20mg/L, are exposed as in Application Example 1 to determine the relativephotopermanence. Loss of compound is monitored by loss of absorbance atlambda max. Results are below. Series A Absorbance Compound 0 h 6 h 12 h18 h ΔA ΔA/100 104 (331 nm) 1.75 1.72 1.65 1.55 0.20 1.11 141 (325 nm)1.32 1.25 1.15 1.07 0.27 1.50Compound 104 is shown to be more stable than 141 in Ethyl Acetatesolution.

Series B Absorbance Compound 0 h 6 h 12 h 18 h 30 h ΔA ΔA/100 141 (325nm) 1.18 1.07 0.93 0.84 0.70 0.48 1.60 3,4,5-tri (315 nm) 1.00 0.87 0.690.51 0.15 0.85 2.83 PR25 (310 nm) 1.94 1.87 1.80 1.72 1.57 0.37 1.233-mono (278 nm) 2.20 1.95 1.83 1.70 1.48 0.72 2.40 2,3-di (283 nm) 1.811.72 1.63 1.55 1.39 0.42 1.40 3,4-di (327 nm) 1.80 1.74 1.63 1.58 1.410.37 1.23

The trimethoxy compound 141 of this invention is more red shifted andmore stable in ethyl acetate solution than the trimethoxy compound ofU.S. Pat. No. 5,882,624.

The 3,4,5-tri compound is not as stable as the 2,4,6-tri compound(compound 141). An indirect comparison shows that the 2,3-di and 3,4-dicompounds are not as stable as the 2,4-di compound (compound 104).

Polymethyl(methacrylate) Films

Polymethyl (methacrylate) films, 1 mil thick, are cast from roomtemperature methylene chloride solutions of polymethyl (methacrylate),medium molecular weight, Aldrich and between 1 and 3% benzylidenemalonate derivative (wt % based on polymer) using a calibrated drawdownbar. The free standing films are mounted in cardboard holders, securedin metal frames and exposed in an Atlas Ci65 xenon arc weatherometerunder dry conditions (ASTM G26). Loss of UVA is determined by monitoringloss of diagnostic UV absorbance. To eliminate scatter due to excessivenoise in the UV spectra at 0 hours, data on rate loss is tabulatedbeginning at 1000 hours after a smooth loss rate is observed andmeasured at 300, 310 and 320 nm rather than only at lambda max. PR25,1.4% Absorbance wavelength (nm) 1000 h 1500 h 2000 h ΔA ΔA/100 300 2.952.67 2.37 0.58 0.06 310 3.21 3.06 2.77 0.44 0.04 320 3.19 2.86 2.51 0.680.07

Compound 104 1.57% Absorbance wavelength (nm) 1000 h 1500 h 2000 h ΔAΔA/100 300 2.97 2.76 2.51 0.46 0.05 310 3.12 2.89 2.65 0.47 0.05 3203.77 3.55 3.23 0.54 0.05

Compound 141, 1.74% Absorbance wavelength (nm) 1000 h 1500 h 2000 h ΔAΔA/100 300 2.35 2.27 2.16 0.19 0.02 310 3.14 3.02 2.93 0.21 0.02 3203.53 3.33 3.23 0.30 0.03

The compounds of the instant invention, 104 and 141 are as stable ormore stable in PMMA than the commercial benzylidene malonate PR25.

The combined data from the above examples demonstrates the desirablespectral and durabilty chartacteristics of the di and tri substitutedbenzylidene malonates substituted at the 2-position vs. thosesubstituted at the 3-position.

The compounds employed are:

PR25, dimethyl p-methoxybenzylidenemalonate (CAS# 7443-25-6)

1. A composition comprising (a) an organic polymer or recording materialsubject to the adverse effects of ultraviolet light, and (b) at leastone benzoxazinone compound of the formula

where each R and R′ is independently hydrogen, halogen, straight orbranched chain alkoxy of 1 to 24 carbon atoms, cycloalkoxy of 5 to 12carbon atoms, perfluoroalkoxy of 1 to 24 carbon atoms, cyano,perfluoroalkyl of 1 to 12 carbon atoms, —CO-G₃, —COOG₃, —CONHG₃,—CON(G₃)₂, E₃S—, E₃SO—, E₃SO₂—, nitro, —N(G₃)₂, G₃ is hydrogen, straightor branched chain alkyl of 1 to 24 carbon atoms, straight or branchedchain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbonatoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 12 carbonatoms, or said aryl or said phenylalkyl substituted on the aryl ring by1 to 4 alkyl of 1 to 4 carbon atoms, or each R and R′ is independentlyhydroxy, straight or branched chain alkyl of 1 to 24 carbon atoms,straight or branched chain alkenyl of 2 to 24 carbon atoms, cycloalkylof 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6to 12 carbon atoms, or said aryl or said phenylalkyl substituted on thearyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms; or each R and R′ isindependently said alkyl of 1 to 24 carbon atoms or said alkoxy of 1 to24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted byone or more —OH, —COOG₃, —OCOG₃, —OE₄, —NCO, —NHCOG₃ or —NE₇E₈ groups ormixtures thereof, where E₄ is straight or branched chain alkyl of 1 to24 carbon atoms or straight or branched chain alkenyl of 2 to 18 carbonatoms; or said alkyl or said alkenyl interrupted by one or more —O—,—NH— or —NE₄- groups or mixtures thereof and which can be unsubstitutedor substituted by one or more —OH, —NH₂ or —COOG₃ or mixtures thereof,or each R and R′ is independently a group of formula

where E₂₂, E₂₃, E₂₄, E₂₅ and E₂₆ are independently hydrogen, halogen,straight or branched alkyl of 1 to 18 carbon atoms, alkenyl of 2 to 18carbon atoms, said alkyl or said alkenyl substituted by one or morehalogen, —OCOG₃, —OE₄, —NCO, —NHCOG₃ or —NE₇E₈, or mixtures thereof,where E₄ is straight or branched chain alkyl of 1 to 24 carbon atoms orstraight or branched chain alkenyl of 2 to 18 carbon atoms; or saidalkyl or said alkenyl interrupted by one or more —O—, —NH— or —NE₄-groups or mixtures thereof and which can be unsubstituted or substitutedby one or more —OH, or —NH₂, or mixtures thereof; or E₂₂, E₂₃, E₂₄, E₂₅and E₂₆ are independently phenyl, phenylalkyl of 7 to 15 carbon atoms,—OH, —OCOG₃, —OE₃, —NCO, —NHCOG₃ or —NE₇E₈, cyano, nitro, perfluoroalkylof 1 to 12 carbon atoms, —COG₃, —COOG₃, —CON(G₃)₂, —CONHG₃, E₃S—, E₃SO—,E₃SO₂—, —SO₂—X₁-E₃; X₁ is —O—, —NH— or —NE₄-; E₃ is alkyl of 1 to 20carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, alkenyl of 3 to 18carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15carbon atoms, aryl of 6 to 12 carbon atoms or said aryl substituted byone or two alkyl of 1 to 4 carbon atoms or1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6to 16 carbon atoms, E₇ and E₈ are independently hydrogen, alkyl of 1 to18 carbon atoms, C₆-C₁₄aryl, C₇-C₁₅aralkyl, straight or branched chainalkenyl of 2 to 18 carbon atoms, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl orC₁-C₃hydroxylalkyl, or E₇ and E₈ together with the N atom are apyrrolidine, piperidine, piperazine or morpholine ring, where at leastone R is halogen, cyano, perfluoroalkyl of 1 to 12 carbon atoms, —CO-G₃,—COOG₃, —CONHG₃, —CON(G₃)₂, E₃SO—, E₃SO₂—, nitro or a group

where at least one of E₂₂-E₂₆ is halogen, cyano, perfluoroalkyl of 1 to12 carbon atoms, —CO-G₃, —COOG₃, —CONHG₃, —CON(G₃)₂, E₃SO—, E₃SO₂— ornitro.
 2. A composition according to claim 1 where one of R is nitro,E₃SO₂—, —CO-G₃, —COOG₃, —CONHG₃ or —CON(G₃)₂.
 3. A composition accordingto claim 1 where at least one of R is —CF₃.